Methods for synthesizing submicron doped silicon particles

ABSTRACT

Methods are described that have the capability of producing submicron/nanoscale particles, in some embodiments dispersible, at high production rates. In some embodiments, the methods result in the production of particles with an average diameter less than about 75 nanometers that are produced at a rate of at least about 35 grams per hour. In other embodiments, the particles are highly uniform. These methods can be used to form particle collections and/or powder coatings. Powder coatings and corresponding methods are described based on the deposition of highly uniform submicron/nanoscale particles.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of copending U.S. patent applicationSer. No. 12/152,428, filed on May 13, 2008 to Bi et. al, entitled“Nanoparticle Production and Corresponding Structures,” incorporatedherein by reference, which is a continuation of U.S. patent applicationSer. No. 11/357,711, filed on Feb. 17, 2006 to Bi et al., now abandoned,entitled “Nanoparticle Production and Corresponding Structures,”incorporated herein by reference, which is a divisional of U.S. patentapplication Ser. No. 10/195,851, now U.S. Pat. No. 7,384,680 to Bi etal., entitled “Nanoparticle-Based Powder Coatings And CorrespondingStructures,” incorporated herein by reference, which iscontinuation-in-part of copending U.S. patent application Ser. No.09/606,884 to Bi et al., entitled “Batteries With ElectroactiveNanoparticles,” which is a continuation of U.S. patent application Ser.No. 09/333,099, now U.S. Pat. No. 6,130,007, which is a continuation ofU.S. patent application Ser. No. 08/897,776 now U.S. Pat. No. 5,952,125;U.S. patent application Ser. No. 09/841,255 now U.S. Pat. No. 7,258,706to Kambe et al., entitled “Abrasive Particles For Surface Polishing,”which is a continuation of U.S. patent application Ser. No. 08/961,735now U.S. Pat. No. 6,290,735; U.S. patent application Ser. No.09/558,266, now U.S. Pat. No. 6,890,624 to Kambe et al., entitled“Self-Assembled Structures”; U.S. patent application Ser. No. 08/962,362now U.S. Pat. No. 7,132,783 to Kambe et al., entitled “Phosphors”; U.S.patent application Ser. No. 09/566,476 now abandoned to Kambe et al.,entitled “Ultraviolet Light Block And Photocatalytic Materials,” whichis a divisional of U.S. patent application Ser. No. 08/962,515 now U.S.Pat. No. 6,099,798; U.S. patent application Ser. No. 09/085,514, nowU.S. Pat. No. 6,726,990 to Kumar et al., entitled “Silicon OxideParticles”; copending U.S. patent application Ser. No. 09/136,483 toKumar et al., entitled “Aluminum Oxide Particles”; U.S. patentapplication Ser. No. 09/188,768, now U.S. Pat. No. 6,607,706 to Kumar etal., entitled “Composite Metal Oxide Particles”; U.S. patent applicationSer. No. 09/188,770, now U.S. Pat. No. 6,506,493 to Kumar et al.,entitled “Metal Oxide Particles”; copending U.S. patent application Ser.No. 09/757,519 to Home et al., entitled “Metal Vanadium OxideParticles,” which is a continuation of U.S. patent application Ser. No.09/246,076 now U.S. Pat. No. 6,255,007; U.S. patent application Ser. No.09/266,202, now U.S. Pat. No. 7,423,512 to Reitz et al., entitled “ZincOxide Particles,” which is a continuation-in-part of U.S. patentapplication Ser. No. 08/962,362; U.S. patent application Ser. No.10/113,998, now U.S. Pat. No. 6,749,966 to Reitz et al., entitled “MetalVanadium Oxide Particles” which is a continuation of U.S. patentapplication Ser. No. 09/311,506 now U.S. Pat. No. 6,394,494; U.S. patentapplication Ser. No. 09/334,203, now U.S. Pat. No. 6,482,374 to Kumar etal., entitled “Methods For Producing Lithium Metal Oxide Particles”;U.S. patent application Ser. No. 09/362,631 now abaondoned to Mosso etal. entitled “Particle Production Apparatus”; U.S. patent applicationSer. No. 09/433,202 now abandoned to Reitz et al., entitled “ParticleDispersions,” which is a continuation-in-part of U.S. patent applicationSer. No. 09/136,483; copending U.S. patent application Ser. No.09/435,748 to Buckley et al., entitled “Electrodes”; U.S. patentapplication Ser. No. 09/557,696 now U.S. Pat. No. 7,112,449 to Bi et al.entitled “Combinatorial Chemical Synthesis,” which claims priority toU.S. Provisional application 60/194,734; U.S. patent application Ser.No. 09/595,958, now U.S. Pat. No. 6,749,648 to Kumar et al., entitled“Lithium Metal Oxides”; U.S. patent application Ser. No. 09/649,752, nowU.S. Pat. No. 6,503,646 to Ghantous et al., entitled “High RateBatteries”; U.S. patent application Ser. No. 09/697,697, now U.S. Pat.No. 6,680,041 to Kumar et al., entitled “Metal Oxide Particles,” whichis a divisional of U.S. patent application Ser. No. 09/188,770; U.S.patent application Ser. No. 09/715,935, now U.S. Pat. No. 7,575,784 toBi et al., entitled “Coating Formation By Reactive Deposition”; U.S.patent application Ser. No. 09/731,286, now U.S. Pat. No. 6,471,930 toKambe et al. entitled “Silicon Oxide Particles” which is a divisional ofU.S. patent application Ser. No. 08/961,735 now U.S. Pat. No. 6,290,735;U.S. patent application Ser. No. 09/753,484, now U.S. Pat. No. 6,508,855to Gardner et al. entitled “Reactant Delivery Apparatuses,” which is adivisional of U.S. patent application Ser. No. 09/188,670 now U.S. Pat.No. 6,193,936; U.S. application Ser. No. 09/818,141, now U.S. Pat. No.6,599,631 to Kambe et al. entitled “Polymer Inorganic ParticleComposites,” which claims priority to U.S. Provisional application Ser.No. 60/265,169; U.S. patent application Ser. No. 09/843,195, now U.S.Pat. No. 6,692,660 to Kumar et al., entitled “High Luminescence PhosphorParticles”; copending U.S. patent application Ser. No. 09/845,985 toChaloner-Gill et al., entitled “Phosphate Powder Compositions AndMethods For Forming Particles With Complex Anions”; U.S. patentapplication Ser. No. 09/931,977, now U.S. Pat. No. 6,788,866 to Bryan,entitled “Layer Materials On Substrates”; copending U.S. patentapplication Ser. No. 09/969,025 to Chiruvolu et al., entitled “AluminumOxide Powders”; U.S. patent application Ser. No. 09/970,279, now U.S.Pat. No. 7,507,382 to Reitz et al., entitled “Multiple Reactant Nozzlesfor a Flowing Reactor,” which is a divisional of U.S. patent applicationSer. No. 09/266,202, now U.S. Pat. No. 7,423,512 entitled “Zinc OxideParticles,” which is a continuation-in-part of U.S. patent applicationSer. No. 08/962,362; copending U.S. Provisional Patent application Ser.No. 60/312,234 to Bryan, entitled “Reactive Deposition For The FormationOf Chip Capacitors”; copending U.S. Provisional Patent Application Ser.No. 60/315,438 to Home et al., entitled “Optical Waveguide Preforms”;copending PCT application designating the U.S. serial numberPCT/US01/32413 to Bi et al., entitled “Coating Formation By ReactiveDeposition”; copending PCT application designating the U.S. serialnumber PCT/US01/45762 to Bi et al. entitled “Multilayered OpticalDevices” which claims priority to U.S. provisional application60/243,491; copending PCT application designating the U.S. serial numberPCT/US02/01702 to Bryan et al. entitled “Optical Material With SelectedIndex Of Refraction” which claims priority to U.S. Provisionalapplication 60/262,274 and U.S. Provisional application 60/262,273; U.S.patent application Ser. No. 10/027,906, now U.S. Pat. No. 6,952,504 toBi et al., entitled “Three Dimensional Engineering Of Planar OpticalStructures”; U.S. patent application Ser. No. 10/076,976 now abandonedto Bi et al., entitled “Titanium Oxide Nanoparticles,” which is acontinuation of U.S. patent application Ser. No. 09/123,255 now U.S.Pat. No. 6,387,531, entitled “Metal (Silicon) Oxide/Carbon CompositeParticles”; U.S. patent application Ser. No. 10/083,967 now U.S. Pat.No. 7,226,966 to Kambe et al., entitled “Structures IncorporatingPolymer-Inorganic Particle Blends,” which claims priority to U.S.Provisional patent application Ser. No. 60/309,887; U.S. applicationSer. No. 10/138,754 now U.S. Pat. No. 7,164,818 to Bryan et al. entitled“Integrated Gradient Index Lenses” which claims priority to U.S.provisional application 60/288,533; and 10/099,597 to Home et al., filedon Mar. 15, 2002, now U.S. Pat. No. 6,849,334, entitled “OpticalMaterials And Optical Devices,” which claims priority to U.S.provisional application 60/313,588; and U.S. patent application Ser. No.10/119,645, now U.S. Pat. No. 6,919,054 to Gardner et al., entitled“Reactant Nozzles Within Flowing Reactors,” each of which above isincorporated herein by reference.

FIELD OF THE INVENTION

This application relates to high rate production of submicron/nanoscaleparticles, especially high uniformity particles that are generallyun-fused. In addition, this application relates to structures, such aspowder coatings, formed with submicron/nano scale particles with highuniformity.

BACKGROUND OF THE INVENTION

Advances in a variety of fields have created a demand for many types ofnew materials. In particular, a variety of chemical powders can be usedin many different processing contexts, such as the production ofelectrical components, optical components, electro-optical componentsand batteries. Similarly, technological advances have increased thedemand for improved material processing with strict tolerances onprocessing parameters. As miniaturization continues even further,material parameters will need to fall within stricter tolerances.Current integrated circuit technology already requires tolerances onprocessing dimensions on a submicron scale.

The consolidation or integration of mechanical, electrical and opticalcomponents into integral devices has created enormous demands onmaterial processing. Furthermore, the individual components integratedin the devices are shrinking in size. Therefore, there is considerableinterest in the formation of specific compositions applied tosubstrates.

An explosion of communication and information technologies includinginternet based systems has motivated a world wide effort to implementoptical communication networks to take advantage of a large bandwidthavailable with optical communication. The capacity of optical fibertechnology can be expanded further with implementation of DenseWavelength Division Multiplexing technology. With increasing demands,more channels are needed to fulfill the system functions. Integratedplanar components can be used to replace discrete optical components tosupply the desired capacity. To form these integrated structures, thereis considerable interest in the formation of specific compositionsapplied to substrates. In order to form optical devices with highquality optical coatings from these materials, the coating propertiesneed to be specified accordingly.

SUMMARY OF THE INVENTION

In a first aspect, the invention pertains to methods for producingproduct particles comprising an inorganic composition. The productparticles have an average particle size of no more than about 75 nm. Themethods comprise reacting at least one precursor compound to produce theproduct particles at a rate of at least about 35 grams per hour.Particles refer to dispersible units within the collection of particles,while primary particles refer to distinguishable units in a transmissionelectron micrograph, as described further below. Product particlescomprise a collection of particles and generally have primary particlesidentifiable from appropriate micrographs.

In another aspect, the invention pertains to methods for producingproduct particles comprising an inorganic composition. The productparticles have an average particle size of no more than about 500 nm,and the particles have effectively no particles with a diameter greaterthan about 4 times the average particle size. The methods comprisereacting at least one precursor compound to produce the productparticles at a rate of at least about 35 grams per hour.

Furthermore, the invention pertains to methods for producing productparticles comprising an inorganic composition. The product particleshave an average primary particle size of no more than about 500 nm, andthe primary particles have effectively no particles with a diametergreater than about 4 times the average particle size. The methodscomprise reacting at least one precursor compound to produce the productparticles at a rate of at least about 35 grams per hour.

In a further aspect, the invention pertains to methods for producingproduct particles comprising an inorganic composition. The productparticles have an average particle size of no more than about 500 nm,and the product particles have a distribution of particle sizes in whichat least about 95 percent of the particles have a diameter greater thanabout 60 percent of the average diameter and less than about 140 percentof the average diameter. The methods comprise reacting at least oneprecursor compound to produce the product particles at a rate of atleast about 35 grams per hour.

In additional aspects, the invention pertains to methods for producingproduct particles comprising an inorganic composition. The productparticles have an average primary particle size of no more than about500 nm, and the primary particles have a distribution of particle sizesin which at least about 95 percent of the particles have a diametergreater than about 60 percent of the average diameter and less thanabout 140 percent of the average diameter. The methods comprise reactingat least one precursor compound to produce the product particles at arate of at least about 35 grams per hour.

In addition, the invention pertains to a powder coating comprising aninorganic composition. The coating comprises primary particles having anaverage particle size less than about 500 nm and effectively no primaryparticles having a diameter greater than about 4 times the averageprimary particle diameter.

In other embodiments, the invention pertains to methods for forming apowder coating, the method comprising reacting a flowing reactant streamto form a flow of product particles and depositing the product particleson a substrate from the flow. The flow of product particles has anaverage diameter less than about 500 nanometers and has effectively noparticles with a diameter greater than about 4 times the averagediameter.

In further embodiments, the invention pertains to a collection ofparticles comprising a metal borate wherein the particles have anaverage diameter less than about 500 nm.

The invention further pertains to particle collections and powdercoatings produced by the above methods. The invention further pertainsto products made from particle collections and powder coatings formed bythe above methods and to products made from the powder coatingsdescribed above.

In additional aspects, the invention pertains to methods for producingproduct particles comprising an inorganic composition wherein theproduct particles have an average particle size of no more than about 75nm. The methods comprise a step for producing the product particles at arate of at least about 35 grams per hour.

In further aspects, the invention pertains to methods for producingproduct particles comprising an inorganic composition wherein theproduct particles have an average particle size of no more than about500 nm. The particles have effectively no particles with a diametergreater than about 4 times the average particle size. The methodscomprise a step for producing the product particles at a rate of atleast about 35 grams per hour.

In other aspects, the invention pertains to methods for producingproduct particles comprising an inorganic composition wherein theproduct particles have an average particle size of no more than about500 nm. The product particles have a distribution of particle sizes inwhich at least about 95 percent of the particles have a diameter greaterthan about 60 percent of the average diameter and less than about 140percent of the average diameter. The methods comprise a step forproducing the product particles at a rate of at least about 35 grams perhour.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic, sectional view of an embodiment of a laserpyrolysis apparatus, where the cross section is taken through the middleof a radiation path. The upper insert is a bottom view of a collectionnozzle, and the lower insert is a top view of an injection nozzle.

FIG. 2 is a schematic, side view of an embodiment of a reactant deliveryapparatus for the delivery of vapor reactants to the laser pyrolysisapparatus of FIG. 1.

FIG. 3A is a schematic, sectional view of an alternative embodiment ofthe reactant delivery apparatus for the delivery of an aerosol reactantto the laser pyrolysis apparatus of FIG. 1, the cross section beingtaken through the center of the apparatus.

FIG. 3B is a schematic, sectional view of a reactant delivery apparatuswith two aerosol generators within a single reactant inlet nozzle.

FIG. 4 is a schematic sectional view of an inlet nozzle of a reactantdelivery system for the delivery of both vapor and aerosol reactants inwhich the vapor and aerosol reactants combine within the nozzle.

FIG. 5 is a schematic sectional view of an inlet nozzle of a reactantdelivery system for the delivery of both vapor and aerosol reactants inwhich the vapor and aerosol combine within the reaction chamber prior toreaching a radiation beam.

FIG. 6 is a perspective view of an alternative embodiment of a laserpyrolysis apparatus.

FIG. 7 is a sectional view of an inlet nozzle of the alternative laserpyrolysis apparatus of FIG. 4, the cross section being taken along thelength of the nozzle through its center.

FIG. 8 is a sectional view of an inlet nozzle of the alternative laserpyrolysis apparatus of FIG. 4, the cross section being taken along thewidth of the nozzle through its center.

FIG. 9 is a perspective view of an embodiment of an elongated reactionchamber for performing laser pyrolysis.

FIG. 10 is a perspective view of an embodiment of an elongated reactionchamber for performing laser pyrolysis.

FIG. 11 is a cut away, side view of the reaction chamber of FIG. 10.

FIG. 12 is a partially sectional, side view of the reaction chamber ofFIG. 10, taken along line 12-12 of FIG. 10.

FIG. 13 is a fragmentary, perspective view of an embodiment of areactant nozzle for use with the chamber of FIG. 10.

FIG. 14 is a schematic diagram of a light reactive deposition apparatusformed with a particle production apparatus connected to a separatecoating chamber through a conduit.

FIG. 15 is a perspective view of a coating chamber where the walls ofthe chamber are transparent to permit viewing of the internalcomponents.

FIG. 16 is perspective view of a particle nozzle directed at a substratemounted on a rotating stage.

FIG. 17 is a schematic diagram of a light reactive deposition apparatusin which a particle coating is applied to a substrate within theparticle production chamber.

FIG. 18 is a perspective view of a reactant nozzle delivering reactantsto a reaction zone positioned near a substrate.

FIG. 19 is a sectional view of the apparatus of FIG. 18 taken along line19-19.

FIG. 20 is a perspective view of an embodiment of a light reactivedeposition chamber.

FIG. 21 is an expanded view of the reaction chamber of the lightreactive deposition chamber of FIG. 20.

FIG. 22 is an expanded view of the substrate support of the reactionchamber of FIG. 21.

FIG. 23 is a schematic, sectional view of an apparatus for heat treatingsubmicron/nanoscale particles, in which the section is taken through thecenter of the apparatus.

FIG. 24 is a schematic, sectional view of an oven for heatingsubmicron/nanoscale particles, in which the section is taken through thecenter of a tube.

FIG. 25 is a sectional side view of an apparatus for introducingdopant(s)/additive(s) by electro-migration deposition.

FIG. 26 is a top view of a device configured for electro-migrationdeposition over a portion of a substrate.

FIG. 27 is an x-ray diffractogram of amorphous V₂O₅ nanoparticles.

FIG. 28 is an x-ray diffractogram of 2-D crystals of V₂O₅ nanoparticles.

FIG. 29 is a transmission electron microscope view of amorphous V₂O₅nanoparticles.

FIG. 30 is an x-ray diffractogram of crystalline VO₂ nanoparticles.

FIG. 31 is a transmission electron microscope view of crystalline VO₂nanoparticles at higher magnification.

FIG. 32 is a transmission electron microscope view of crystalline VO₂nanoparticles at lower magnification.

FIG. 33 is a plot depicting the distribution of particle sizes for thecrystalline VO₂ nanoparticles depicted in FIGS. 31 and 32.

FIG. 34 is an x-ray diffractogram of crystalline VO_(1.27)nanoparticles.

FIG. 35 is an x-ray diffractogram of V₆O₁₃/VO₂ mixed phasenanoparticles.

FIG. 36 is an x-ray diffractogram of VO₂/V₂O₃ mixed phase nanoparticles.

FIG. 37 is an x-ray diffractogram of single phase crystalline V₂O₅nanoparticles.

FIG. 38 is an x-ray diffractogram of single phase crystalline V₂O₅nanoparticles produced using different starting materials than used toproduce the particles which generated the diffractogram in FIG. 37.

FIG. 39 is an x-ray diffractogram of silicon oxide nanoparticles.

FIG. 40 is a TEM micrograph of nanoparticles whose x-ray diffractogramis shown of FIG. 39.

FIG. 41 is a plot of the distribution of primary particle diameters forthe nanoparticles shown in the TEM micrograph of FIG. 40.

FIG. 42 is an x-ray diffractogram of nanoparticles of silicon oxidefollowing heating in an oven.

FIG. 43 is a TEM micrograph of silicon oxide nanoparticles followingheat treatment in an oven.

FIG. 44 is an x-ray diffractogram of nanoparticles of lithiatedmanganese oxide produced by laser pyrolysis of a reactant stream with anaerosol.

FIG. 45 is an x-ray diffractogram of nanoparticles of lithiatedmanganese oxide following heating in an oven.

FIG. 46 is an x-ray diffractogram for a sample of lithium manganeseoxide particles directly produced by laser pyrolysis.

FIG. 47 is a transmission electron micrograph of lithium manganese oxideparticles corresponding to the x-ray diffractogram of FIG. 46.

FIG. 48 is a plot of two x-ray diffractograms of mixed phase materialsincluding silver vanadium oxide nanoparticles produced directly by laserpyrolysis, where each plot is produced with materials produced underslightly different conditions.

FIG. 49 is a plot of four x-ray diffractograms of silver vanadium oxideproduced by heat treating nanocrystalline V₂O₅ with silver nitrate in anoxygen atmosphere, where each diffractogram was produced with materialsformed under different conditions.

FIG. 50 is a plot of three x-ray diffractograms of silver vanadium oxideproduced by heat treating nanocrystalline V₂O₅ with silver nitrate in anargon atmosphere, where each diffractogram was produced with materialsformed under different conditions.

FIG. 51 is a transmission electron microscope view of silver vanadiumoxide nanoparticles.

FIG. 52 is a transmission electron microscope view of the V₂O₅nanoparticle samples used to produce the silver vanadium oxide particlesshown in FIG. 51.

FIG. 53 is a plot of two x-ray diffractograms of mixed phase materialsincluding silver vanadium oxide nanoparticles produced directly by laserpyrolysis, where each plot is produced with materials produced underslightly different conditions.

FIG. 54A is a transmission electron micrograph of the materials from thesample corresponding to the upper diffractogram in FIG. 53.

FIG. 54B is a transmission electron micrograph of the materials from thesample corresponding to the lower diffractogram in FIG. 53.

FIG. 55 is an x-ray diffractogram of elemental silver nanoparticlesproduced by laser pyrolysis under the conditions specified in the firstcolumn of Table 8.

FIG. 56 is an x-ray diffractogram of elemental silver nanoparticlesproduced by laser pyrolysis under the conditions specified in the secondcolumn of Table 8.

FIG. 57 is a transmission electron micrograph of the materials from thesample corresponding to the diffractogram in FIG. 55.

FIG. 58 is an x-ray diffractogram of silicon nitride nanoparticlesproduced by laser pyrolysis.

FIG. 59 is two transmission electron micrographs of silicon nitridenanoparticles equivalent to those used to produce the x-raydiffractogram of FIG. 58.

FIG. 60 is a particle size distribution obtained from the micrograph inFIG. 59.

FIG. 61 is an x-ray diffractogram of silicon carbide nanoparticlesproduced by laser pyrolysis.

FIG. 62 is a transmission electron micrograph of silicon carbidenanoparticles equivalent of those used to produce the x-raydiffractogram of FIG. 61.

FIG. 63 is a particle size distribution obtained from the micrograph ofFIG. 62.

FIG. 64 is a x-ray diffractogram of a sample of lithium iron phosphateproduced by laser pyrolysis under one set of conditions.

FIG. 65 is a transmission electron micrograph of a sample of lithiumiron phosphate produced by laser pyrolysis.

FIG. 66 is an x-ray diffractogram of a sample of europium doped bariummagnesium aluminum oxide produced by laser pyrolysis.

FIG. 67 is an x-ray diffractogram of a sample of europium doped bariummagnesium aluminum oxide produced by laser pyrolysis produced underdifferent conditions that used to produce the sample of FIG. 66.

FIG. 68 is an x-ray diffractogram of a first sample produced by laserpyrolysis following a heat treatment.

FIG. 69 is an x-ray diffractogram of a second sample produced by laserpyrolysis following a heat treatment.

FIG. 70 is a transmission electron micrograph of a powder used togenerate the x-ray diffractogram in FIG. 68.

FIG. 71 is an x-ray diffractogram of two samples of(Y_(0.95)Eu_(0.05))₂O₃ produced by laser pyrolysis.

FIG. 72 is an x-ray diffractogram of lithium cobalt oxide nanoparticlesproduced by laser pyrolysis with gaseous reactants according to theparameters specified in column 1 of Table 14.

FIG. 73 is an x-ray diffractogram of crystalline lithium cobalt oxidenanoparticles produced by heat treating lithium cobalt oxide precursornanoparticles.

FIG. 74 is a transmission electron microscopy (TEM) micrograph of thecrystalline lithium cobalt oxide nanoparticles.

FIG. 75 is a particle size distribution produced from the micrograph ofFIG. 74.

FIG. 76 is an x-ray diffractogram of lithium nickel oxide precursornanoparticles produced by laser pyrolysis according to parametersspecified in Table 16.

FIG. 77 is an x-ray diffractogram of crystalline lithium nickel oxidenanoparticles produced by heat treating lithium nickel oxide precursornanoparticles.

FIG. 78 is an x-ray diffractogram of lithium nickel cobalt oxidenanoparticles produced by laser pyrolysis according to parametersspecified in Table 17.

FIG. 79 is an x-ray diffractogram of crystalline lithium nickel cobaltoxide nanoparticles produced by heat treating lithium nickel cobaltoxide precursor nanoparticles.

FIG. 80 is an x-ray diffractogram of titanium dioxide nanoparticles.

FIG. 81 is a transmission electron micrograph of titanium dioxidenanoparticles.

FIG. 82 is a plot of x-ray diffractograms for lithium titanium oxidesproduced from commercial titanium dioxide (upper curve) andnanoparticles of titanium dioxide (lower curve).

FIG. 83 is a transmission electron micrograph of nanoparticles oflithium titanium oxide with a stoichiometry of Li₄Ti₅O₁₂.

FIG. 84 is a plot of five x-ray diffractograms for samples of aluminumoxide produced by laser pyrolysis produced with either vapor reactantsor aerosol reactants. A line plot of the diffractogram peaks fordelta-aluminum oxide is presented in the lower insert for comparison.

FIG. 85 is a transmission electron micrograph of a sample of aluminumoxide produced by laser pyrolysis with aerosol reactants.

FIG. 86 is a transmission electron micrograph of a sample of aluminumoxide particles produced by laser pyrolysis with vapor reactants.

FIG. 87 is a transmission electron micrograph of another sample ofaluminum oxide particles produced by laser pyrolysis with vaporreactants.

FIG. 88 is a plot of an x-ray diffractogram for a sample of aluminumoxide particles following a heat treatment (upper curve) and acorresponding sample prior to heat treatment (lower plot) produced bylaser pyrolysis with aerosol reactants. For comparison, a line plot ofthe diffractogram peaks for three phases of aluminum oxide are presentedin the bottom of the figure.

FIG. 89 is a transmission electron micrograph of a sample of aluminumoxide particles following heat treatment in which the sample, prior toheat treatment, was produced by laser pyrolysis with aerosol reactants.

FIG. 90 is a plot of an x-ray diffractogram for three samples ofaluminum oxide particles following a heat treatment (upper curves) and arepresentative sample prior to heat treatment (lower plot) produced bylaser pyrolysis with vapor reactants. For comparison, a line plot of thediffractogram peaks for three phases of aluminum oxide are presented inthe bottom of the figure.

FIG. 91 is a transmission electron micrograph of a sample of aluminumoxide particles following heat treatment in which the sample, prior toheat treatment, was produced by laser pyrolysis with vapor reactants.

FIG. 92 is a plot of x-ray diffractograms for a sample of alpha-aluminumoxide (lower curve) and for a sample of alpha-aluminum oxide followingthe heat treatment of delta-aluminum oxide produced by laser pyrolysiswith vapor reactants (upper curve). For comparison, a line plot of thediffractogram peaks for two phases of aluminum oxide are presented inthe bottom of the figure.

FIG. 93 is an x-ray diffractogram of zinc oxide nanoparticles producedby laser pyrolysis.

FIG. 94 is a TEM micrograph of nanoparticles whose x-ray diffractogramis shown of FIG. 93.

FIG. 95 is a plot of the distribution of primary particle diameters forthe nanoparticles shown in the TEM micrograph of FIG. 94.

FIG. 96 is an x-ray diffractogram of SnO_(x) nanoparticles.

FIG. 97 is a TEM micrograph of nanoparticles used for the diffractogramof FIG. 96.

FIG. 98 is a plot of the distribution of particle diameters for thenanoparticles based on the micrograph of FIG. 97.

FIG. 99 is a plot indicating the position of x-ray diffraction peaksresulting from tin oxide in FIG. 96, with contributions from SnCl₂ beingremoved.

FIG. 100 is an x-ray diffractogram of SnO_(x) nanoparticles of Example29.

FIG. 101 is a TEM micrograph of nanoparticles of Example 29.

FIG. 102 is an x-ray diffractogram of SnO_(x) nanoparticles of Example30.

FIG. 103 is a TEM micrograph of nanoparticles of Example 30.

FIG. 104 is an x-ray diffractogram of SnO₂ nanoparticles of Example 31.

FIG. 105 is a TEM micrograph of nanoparticles of Example 31.

FIG. 106 is a plot of the distribution of particle diameters for thenanoparticles of Example 31 based on the micrograph of FIG. 105.

DETAILED DESCRIPTION OF THE INVENTION

Submicron/nanoscale particles with excellent properties can be producedat high rates. The high rate submicron/nanoscale particle productiongenerally involves a chemical reaction within a flow originating from areactant inlet nozzle, although other methods based on a chemicalreaction can be used to produce particles. In particular, rates of atleast about 35 grams per hour (g/h) can be achieved. Specifically,particles with average particle sizes less than about 75 nanometers (nm)as well as larger particles can be produced at high rates. In someembodiments, the particles have very high uniformity in particle size,e.g., a narrow particle size distribution as measured by width of thepeak or the lack of a tail in the distribution at larger particle sizes.In addition, powder coatings/powder coatings can be formed with uniquecharacteristics due to small primary particle size and the uniformity ofthe primary particle size, in which the primary particles strike asurface to form the powder coating.

In some embodiments, radiation, e.g., as a radiation beam, intersectsthe reactant flow to drive the reaction. The formation of a well definedreaction zone involving the region at which the radiation intersects thereactant flow can result in the formation of substantially uniformlysized particles. The reaction conditions can be established such thatunfused particles are formed within the flow even at the high particleproduction rates. An elongated reactant inlet nozzle can be used toachieve high throughput through the reaction zone while having theradiation intersect with a significant fraction or all of the reactantflow to obtain high yields. The particles can be deposited onto asubstrate to form powder coatings.

Generally, the flowing reaction approaches discussed herein incorporatea reactant flow that can comprise vapor(s), aerosol(s) or combinationsthereof to introduce desired elements into the flow stream. In addition,selection of the reaction conditions can correspondingly vary the natureof the resulting reaction product. Thus, a tremendous versatility hasbeen achieved with respect to the production of desirable inorganicmaterials, such as amorphous particles, crystalline particles,combinations thereof and corresponding coatings. In addition, treatmentof the particles or coatings following formation can be used to modifythe nature of the materials, for example, the composition and/or crystalstructure, which may not alter significantly the character of thematerials, such as the average particle size, if the treatment isappropriately selected. Coatings can be densified or consolidated into auniform material with approximately uniform density through thematerial.

Some of the principles underlying laser pyrolysis can be adapted fordirectly forming a coating. The resulting coating process is aradiation-based reactive deposition. Specifically, a process has beendeveloped, termed light reactive deposition, to form highly uniformcoatings and structures from a reactive flow. Light reactive depositioninvolves a radiation driven, e.g., laser driven, flowing reactorconfigured for the immediate deposition of particles onto a surface,i.e., without collecting the particles as a separate powder. As withlaser pyrolysis, the reactants are directed from a reactant source intoa flow that proceeds to a reaction zone formed by the intersection ofradiation with the flow. The reactants can be reacted in the flow toform product particles within the flow, which can be subsequentlydeposited on a substrate surface from the flow. The resulting coatingcan be termed a powder coating, which can range in properties from astack of unfused particles to a porous network of fused particles. Thedeposition can be performed within the reaction chamber or in a coatingchamber operably connected to the reaction chamber.

Reactant delivery approaches developed for laser pyrolysis can beadapted for light reactive deposition. In particular, a wide range ofreaction precursors can be used in gaseous/vapor and/or aerosol form,and a wide range of highly uniform product particles can be efficientlyproduced for the deposition in the form of a coating, such as a powdercoating. Specifically, light reactive deposition can be used to formhighly uniform coatings of materials, optionally comprisingdopant(s)/additive(s) and/or complex composition(s). The coating formedby light reactive deposition can be a collection of particles on asurface or a powder coating, depending on the deposition conditions. Forconvenience, this application refers interchangeably to radiation-drivenpyrolysis, light-driven pyrolysis and laser pyrolysis. For convenience,this application also refers interchangeably to radiation-based reactivedeposition and light reactive deposition. In other words, as usedherein, laser pyrolysis and light reactive deposition refer generally toall radiation based particle synthesis and radiation based coatingapproaches, respectively, unless explicitly indicated otherwise. Apowder coating is a network on a substrate of fused, partly fused orun-fused particles in which at least some characteristics of the initialprimary particles are reflected within the coating.

Submicron/nanoscale inorganic particles and corresponding coatings withvarious stoichiometries, sizes and crystal structures can be produced bya variety of reaction methodologies and have been produced by chemicalreaction with flowing reactants, especially by laser pyrolysis/lightreactive deposition using an intense radiation, alone or with additionalprocessing. Specifically, it has been discovered thatsubmicron/nanoscale particles with a range of compositions can beproduced, optionally, with selected dopant(s)/additive(s), such as rareearth metal(s) and/or other elements. In addition, dopant(s)/additive(s)generally can be introduced at desired amounts by varying thecomposition of the reactant stream. Also, modifying element(s), such asdopant(s)/additive(s), can be introduced into an appropriate hostmaterial following formation of particles or a powder coating.

Specifically, with respect to particles, collections of particles ofparticular interest have an average primary particle diameter less thana micron. Collections of particles, as distinguished from coatings,refer to substantially un-fused primary particles that can becorrespondingly dispersed under appropriate conditions. Particlesproduced in a radiation driven reactor can have high uniformity withrespect to composition and particle size, such as a lack of particleswith sizes much larger than the average particle size and/or a narrowdistribution of particle diameters around the average diameter. Inparticular, radiation-driven pyrolysis has been found to be a valuableprocess for efficiently producing submicron (in the range(s) of lessthan about 1 micron average diameter) and nanoscale (in the range(s) ofless than about 100 nanometer (nm) average diameter) particles with highuniformity at high production rates.

In some embodiments, the reactor apparatus, e.g., a laser pyrolysisapparatus or a light reactive deposition apparatus, includes an extendedreactant inlet such that a stream of particles is generated within aflowing sheet forming a reactant/product stream. Generally, the reactantflow is oriented to intersect the radiation such that most or all of thereactant flow intersects with the radiation such that high yields areobtained. Using an extended reactant inlet, a line or stripe ofparticles at a high throughput can be collected or simultaneouslydeposited onto a substrate. It has been discovered how to obtain highreactant throughput such that a high particle production rate can bemaintained without sacrificing control of the product particleproperties or uniformity of the particles and/or the deposited powdercoating. For coating embodiments, by depositing a line or stripe ofparticles, the coating process can be performed more rapidly.

More specifically, in a reactor with an elongated reactant inlet,particle production rates are readily achievable in the range(s) of atleast about 50 grams per hour (g/h) and in other embodiments in therange(s) of at least about 100 g/h. These rates can be used to achieveparticles with a wide range of compositions and with high particleuniformity. Specifically, collections of particles can be formed with adistribution of particle diameters that is highly peaked at or near theaverage such that the distribution of a majority of the particles isnarrow and that has a cut off in the tail of the distribution such thateffectively no particles have a diameter larger than a cut off value ofa low multiple of the average diameter. Corresponding high coating ratesalso can be achieved. The uniformity of the particles in the flow canresult in desirable properties for the corresponding coating formed fromthe particles.

Light reactive deposition has considerable advantages for the productionof particles for coating substrate surfaces. First, light reactivedeposition can be used in the production of a large range of productparticles. Thus, the composition of the corresponding coating can beadjusted based on the features of the light reactive depositionapproach. Furthermore, light reactive deposition can produce very smallparticles with a high production rate. When small particles are coatedonto the surface of the substrate, a smoother coating with a moreuniform thickness can be generated if particle packing is not an issue.

Because of the achievability of high chemical and physical uniformity ofsubmicron/nanoscale product particles, laser pyrolysis is a desirableapproach for producing submicron/nanoscale particles, such as particleswith simple compositions or complex compositions. However, otherapproaches involving flowing reactant streams can be used to synthesizesubmicron/nanoscale particles based on the disclosure herein.Alternative approaches include, for example, flame pyrolysis and thermalpyrolysis. The approaches for particle formation have the commoncharacteristic that the reactants are fed into a flow (possibly withother compositions, such as inert gas and radiation absorbers), whichreactants are then reacted to generate product particles in a continuousproduction process. The product particles within the flow are directedto a collector and/or substrate surface for coating, which results inthe removal of the product particles from the flow. While the productparticles are produced within a flow, the composition and othercharacteristics of the product particles can be modified prior to,during or following removal of the particles from the flow.

Flame pyrolysis can be performed with a hydrogen-oxygen flame, whereinthe flame supplies the energy to drive the pyrolysis. Such a flamepyrolysis approach should produce some of the materials, which can beproduced by the laser pyrolysis techniques herein, except that flamepyrolysis approaches generally do not produce comparable high uniformityand a narrow particle size distribution that can be obtained by laserpyrolysis, which has a well defined reaction zone. Furthermore, flamepyrolysis is restricted with respect to the product compositions by thechemistry of the flame. In addition, flame pyrolysis typically does nothave production rates comparable to high production rates obtainablewith high rate laser pyrolysis systems. A flame production apparatusused to produce oxides is described in U.S. Pat. No. 5,447,708 to Helbleet al., entitled “Apparatus for Producing Nanoscale Ceramic Particles,”incorporated herein by reference. Furthermore, submicron/nanoscale dopedamorphous particles can be produced by adapting inventive reactantdelivery aspects of the laser pyrolysis methods with a thermal reactionchamber such as the apparatus described in U.S. Pat. No. 4,842,832 toInoue et al., “Ultrafine Spherical Particles of Metal Oxide and a Methodfor the Production Thereof,” incorporated herein by reference. Relativeto other approaches, laser pyrolysis has an external heating sourcede-coupled from the reaction chemistry, which results in a greatlyexpanded range of compositions that can be produced by the method.

One feature of applying laser pyrolysis/light reactive deposition forthe production of desired particles/coatings, e.g., doped particles andparticles with complex compositions, can be production of a reactantstream comprising suitable amounts of appropriate host precursor(s) anddopant(s)/additive(s) precursor(s), if any. Similarly, the reactantstream can further comprise an additional radiation absorber,optionally, for example, when one or more of the precursor(s) is anappropriate radiation absorber. Other additional reactants can be usedto adjust the oxidizing/reducing environment in the reactant stream.Inert gases can be added to the reactant flow as carrier gases and/orreaction moderators.

In laser pyrolysis/light reactive deposition, the reactant stream can bepyrolyzed by an intense radiation beam, such as a laser beam. While alaser beam is a convenient energy source, other intense electromagneticradiation (e.g., light) sources can be used in laser pyrolysis/lightreactive deposition. Laser pyrolysis/light reactive deposition providesfor formation of phases of materials that can be difficult to form underthermodynamic equilibrium conditions. As the reactant stream leaves thelight beam, the product particles are rapidly quenched. The reactionzone in a laser pyrolysis system that forms as a result of theintersection of the laser with the reactant stream involves a chemicalthat is significantly different from that present in other pyrolysisapproaches. This reaction chemistry in laser pyrolysis provides asurprising ability to generate a wide range of compositions within thereaction zone.

To perform laser pyrolysis/light reactive deposition, one or morereactants can be supplied in vapor form. Alternatively or additionally,one or more reactants can be supplied as an aerosol. The use of anaerosol provides for the use of a wider range of precursors for laserpyrolysis/light reactive deposition than are suitable for vapor deliveryonly. In some cases, less expensive precursors can be used with aerosoldelivery. Suitable control of the reaction conditions with the aerosoland/or vapor results in submicron/nanoscale particles with a narrowparticle size distribution. In addition, particles produced by laserpyrolysis can be subjected to heating to alter the particle propertiesand/or to consolidate the coatings, such as a powder coating, into auniform material.

In general, the inorganic particles generally comprise metal and/ormetalloid elements in their elemental form and/or in compounds.Specifically, the inorganic particles can comprise, for example,elemental metal or elemental metalloid, i.e. un-ionized elements such assilver and silicon, metal/metalloid oxides, metal/metalloid nitrides,metal/metalloid carbides, metal/metalloid sulfides, metal/metalloidarsinides, metal/metalloid phosphides, e.g., InP, metal/metalloidselenides, metal/metalloid tellurides, or the like, or combinationsthereof. In addition, there is the capability for producingsubmicron/nano-particulate carbon solids, which can be crystalline,e.g., graphitic, amorphous, or a combination thereof. Elemental carbonmaterials, which can include impurities/dopants, such as hydrogen and/ornitrogen, can be considered inorganic since they are not hydrocarbonbased. Some metal/metalloid oxides are particularly desirable forvarious applications, such as phosphors, electro-active materials forbatteries or optical applications, and/or for their ability toconsolidate into desirable uniform materials.

Complex systems of ternary, quaternary and higher complexity compoundscan also be made. In particular, compounds with multiple metal/metalloidelements can be formed. In addition, metal/metalloid compounds withcomplex anions, such as phosphates, sulfates and silicates can beformed. Also, dopant(s)/additive(s) can be incorporated into thematerials. In summary, a wide range of inorganic compositions can begenerated at high rates based on the approaches described herein.

Furthermore, dopant(s)/additive(s) can be introduced to vary propertiesof the particles, a corresponding uniform layer and/or a powder coating.With respect to uniform layers, incorporation of thedopant(s)/additive(s) into the particles used to form a coating canresult in a distribution of the dopant(s)/additive(s) through thedensified material directly as a result of the powder deposition.Desired dopant(s)/additive(s) can be incorporated into particles/powdercoating by introducing the dopant/additive element(s) into the reactantstream and selecting the reaction conditions appropriately.Alternatively or additionally, one or more dopant/additive can becontacted with the powder or powder coating following deposition butbefore consolidation.

For example, dopant(s)/additive(s) can be introduced to change theindex-of-refraction or processing properties, e.g., flow temperature, ofa material. For optical applications, the index-of-refraction can bevaried to form specific optical devices that operate with light of aselected frequency range. Dopant(s)/additive(s) can also interact withinthe materials. For example, some dopant(s)/additive(s) can be introducedto increase the solubility of other dopant(s)/additive(s). Suitabledopant(s)/additive(s) for some applications include, for example, metalelements, metalloid elements, and combinations thereof. In addition,metal/metalloid oxides can also be doped with fluorine, chlorine,nitrogen and/or carbon, which substitute for oxygen in an oxidecomposition. Other dopant(s)/additive(s) can be added to change theabsorption properties, emission properties, magnetic properties and/orphotosensitivity, e.g., the change of index-of-refraction in response toirradiation with appropriate light.

While laser pyrolysis and light reactive deposition generally can beused to form single phase materials, under some reaction conditionsmultiple phase materials can be formed. Thus, a collection of particlesor a powder coating can comprise, for example, amorphous particles,crystalline particles of a single crystal structure (possibly selectedfrom a plurality of possible crystalline isomorphs with the samechemical composition), crystalline particles with a mixture of crystalstructures and/or amorphous structures, or a combination thereof.Similarly, a collection of particles has approximately uniformstoichiometry/composition or a mixture of stoichiometries/compositions.The reactions conditions generally can be varied to select desiredstoichiometries/compositions and/or phase(s) (e.g., crystal structure orlack thereof) of the product particles or powder coating.

While laser pyrolysis and light reactive deposition are very versatilewith respect to adjustments in the composition of materials formed fromthe process, additional processing after the formation of theparticles/coating can be used to further modify the materials. Inparticular, thermal (e.g., heat or cold) treatment(s) of particles canbe used to alter the stoichiometry/composition and/or the phase(s),e.g., crystal structure(s), of the particles. For example, heattreatments under mild conditions have been used to alter the oxidationstate of metals, alter the crystal structure, improve the crystallinityand/or introduce other metal/metalloid elements into powder, all withoutlarge amounts of sintering of the particles. Powder coatings can bemodified using comparable processing. Similarly, dopant(s)/additive(s)can be introduced into powders and/or powder coatings. In general, thecomposition, along with optional dopant(s)/additive(s) and phase can beselected to produce materials with desired properties generallyassociated with the intended application of the material, as describedfurther below.

While powder coatings and other coatings can be useful as formed, thecoatings can be densified to form substantially uniform materials. Toform a substantially uniform layer, a coating, such as a powder coating,can be consolidated. The substantially uniform layer after consolidationcan be an amorphous layer, a polycrystalline layer, a crystalline layeror any combination thereof. To consolidate the materials, a powdercoating is heated to a temperature above which the particles coalescevia one of several possible densification mechanisms—viscous sintering,vapor-phase sintering, and/or liquid-phase sintering. In general, foramorphous particles, the glass transition temperature serves as a lowerbound whereas the melting temperature serves as an upper bound. Ingeneral, for crystalline particles, temperatures in which adequate vaporpressure forms to transport of matter from the concave particle surface(high vapor pressure) to the convex contact point of neighboringparticles (low vapor pressure) serves as a lower bound whereas themelting temperature serves as an upper bound. At these temperatures, thepowder or powder coating densifies to form a substantially uniform layerof material.

In summary, the composition of a powder/powder coating/coating can beadjusted, among other means, by selection of the chemical composition ofthe flowing reactant stream and the reaction conditions within thereaction chamber. Laser pyrolysis/light reactive deposition undercontrolled reaction conditions can form highly uniform particles, powdercoatings with a structure reflecting the particle uniformity, and highlysmooth substantially uniform coatings generally following consolidation.Additional treatments can be performed following initial formation ofparticles or powder coatings to further select the composition and/orstructures of the materials.

Regardless of specific desirable applications or specific materials, theapproaches described herein for producing submicron/nanoscale particlesat high rates and/or with narrow size distributions are broadlyapplicable to inorganic particles and corresponding powder coatings. Thedescription herein generally relates to all types of inorganicmaterials. However, certain types of materials are of particularinterest due to their usefulness in specific applications. In someembodiments, optical properties are of interest, while in otherembodiments other properties, such as various electrical properties,energy storage properties and mechanical properties, are particularlyrelevant for a particular application. Some of these specific materialsare described further below.

The approaches herein for generating particles, powder coatings anduniform materials are desirable for a variety of applications, such asthe formation of materials having useful optical properties.Specifically, submicron/nanoparticle powders can be useful, for example,as phosphors in displays, abrasives for polishes, catalysts, dielectricmaterials for capacitors, electro-active materials for energy storageapplications, such as batteries and/or battery electrodes, UV absorbers,electro-magnetic shielding, photoactive materials, optical materials,materials for electro-optical devices and/or optical devices, materialsfor solar cells, optical devices and/or electro-optical devices,catalysts, electrical components, such as semiconducting devices and orelectrical conductors, and the like. Powder coatings can be useful forthe formation of high surface area coatings with functional propertiesdetermined by the composition of the coating. Thus, powder coatings canhave many uses even if the material is not consolidated into a uniformmaterial. Furthermore, consolidated coatings of uniform materials havesimilar applications that relate to the composition of the coating.

With respect to the formation of optical and/or electro-optical devices,the powders themselves can be suitable optical materials and,additionally or alternatively, can be incorporated by further processinginto additional optical materials. For example, powders can beincorporated into composites with polymers such that the resultingcomposite has desirable optical properties. Polymer-inorganic particlecomposites are described further in copending and commonly assigned U.S.patent application Ser. No. 09/818,141, now U.S. Pat. No. 6,599,631 toKambe et al., entitled “Polymer-Inorganic Particle Composites,”incorporated herein by reference, and copending and commonly assignedU.S. patent application Ser. No. 10/083,967, now U.S. Pat. No. 7,226,966to Kambe et al., entitled “Structures Incorporating Polymer-InorganicParticle Blends,” incorporated herein by reference.

The consolidated materials also can be used for optical and/orelectro-optical applications as well as various other applicationsinvolving thin, substantially smooth inorganic coatings. With respect tooptical applications, optical components and/or functionality can beintegrated onto a planar chip-type base similar to an electronicintegrated circuit. By placing the optical components and/orfunctionality onto a substrate surface such as a silicon wafer, manyoptical components and/or functionality can be squeezed into a smallfootprint. The selection of substrate material is based on factors, orcombinations of factors, such as thermal expansion, cost, strength,compatibility with film/coating material, as well as optical properties.The only fundamental requirement for a substrate material is the abilityto withstand processing temperatures. Other possible substrate materialsinclude, but are not limited to: fused silica, quartz, alumina, lithiumtantalate, lithium niobate, gallium arsenide, indium phosphide,soda-lime silicate glass, borosilicate glass, and aluminosilicate glass.

The optical materials on the substrate surface can be fashioned intospecific devices. In particular, a promising technology for theintegration of optical components centers around the production ofplanar waveguides. Semiconductor processing approaches have been adaptedto form the waveguides following the deposition of optical materials.The formation of integrated optical devices using light reactivedeposition is described further in copending and commonly assigned U.S.patent application Ser. No. 10/027,906, now U.S. Pat. No. 6,952,504 toBi et al., entitled “Three Dimensional Engineering of OpticalStructures,” incorporated herein by reference. The powder coatings canbe also used for forming upon consolidation optical fiber preforms and,by processing of the optical fiber preforms, optical fibers. Thestructure and composition(s) of the preforms and fibers can be selectedto have desired optical properties. Optical fiber preforms are describedfurther, for example, in copending U.S. provisional application Ser. No.60/315,438 to Home et al., entitled “Optical Waveguide Preforms,” andPCT application designating the U.S. serial number PCT/US01/45762 to Biet al., entitled “Multilayered Optical Structures,” both of which areincorporated herein by reference.

In some embodiments, the optical properties of the materials can besignificant for their application even if the materials are not used foroptical communications channels through waveguides/fibers. For example,for the formation of displays and the like, phosphor particles can beused. Phosphor particles generally comprise a host crystalline material,such as ZnO and ZnS, that has desired optical properties, which canfurther comprise a dopant/additive to increase the luminescence and/orshift the emission frequency. For ultaviolet blocks and photocatalyticmaterials, compositions that absorb electromagnetic radiation in theultraviolet part of the spectrum can be useful. Suitable ultravioletabsorbing compositions include, for example, TiO₂ and ZnO. In theproduction of some embodiments of solar cells, carbon particles, such aslaser black and fullerenes, can be used as electron acceptors, asdescribed further in U.S. Pat. No. 5,986,206 to Kambe et al., entitled“Solar Cell,” incorporated herein by reference.

Optical materials can be placed in periodic or approximately periodicarrays to form photonic band gap materials, e.g., photonic crystals. Theperiodicity of the materials results in a corresponding periodicity inindex-of-refraction that can extend in one, two or three dimensions.Photonic crystals can provide a frequency gap covering a range offrequencies of electromagnetic radiation that cannot propagate for anywavevector, i.e., in any direction, including spontaneous emission.Light can be introduced into a photonic crystal by applying light at anangle to the periodic lattice. The frequency gap depends on, forexample, the unit cell size, the crystallographic orientation of theperiodic structure, the indices-of-refraction including the differencesin index between different materials of the lattice and other opticalproperties. Defects can be introduced into the photonic crystal toprovide for electromagnetic propagation within the forbidden band gap.The defects introduce broken symmetry that interrupts the periodicity.The periodicity can be produced, for example, using self-assembly asdescribed further in copending U.S. patent application Ser. No.09/558,266, now U.S. Pat. No. 6,890,624 to Kambe et al., entitled“Self-Assembled Structures,” incorporated herein by reference.Similarly, particles can be incorporated into particle-inorganicparticle blends for self-assembly or other organization into periodicstructures, as described further in copending U.S. patent applicationSer. No. 10/083,967, now U.S. Pat. No. 7,226,966 to Kambe et al.,entitled “Structures Incorporating Polymer-Inorganic Particle Blends,”incorporated herein by reference.

Materials for non-optical applications can be similarly selected to havedesired properties. For example, abrasive particles can be used forchemical-mechanical polishing to produce very smooth surfaces based onthe uniformity and dispersability of the particles. The hardness andchemical properties of the particles generally is selected based on thecharacter of the surface to be polished, and suitable abrasive particlesinclude, for example, SiO₂, CeO₂, TiO₂ and Al₂O₃. For electromagneticshielding applications, magnetic particles can be used effectively, suchas particles comprising Fe₂O₃, Fe₃O₄, Fe₃C and Fe₇C₃. Due to the highsurface area of submicron/nanoscale particles, these particles can haveadvantages for catalyst applications. Compositions for catalystparticles generally depend on the particular catalytic function. Manyinorganic materials, such as metal oxides (e.g., Al₂O₃) and metalparticles (e.g., the noble metals), have commercially significantcatalytic function.

Furthermore, submicron and nanoscale particles can have desirableproperties for energy storage applications, such as for the formation ofbatteries, battery electrodes, and the like. The particles can functionas electro-active materials and/or as electrically conductive materials.Suitable electrically conductive materials include for example metalparticles. Electro-active particles in general can undergoreduction-oxidation reactions. In some embodiments, lithium-basedbatteries are of interest. In some lithium-based batteries, the cathodecomprises a compound that can incorporate lithium ions within thematerial as elemental lithium while the anode comprises elementallithium that oxidizes to lithium ions. It has been found that vanadiumoxides submicron/nanoscale particles have surprisingly high energydensities in lithium-based batteries, as described in U.S. Pat. Nos.5,952,125 and 6,130,007 to Bi et al., entitled “Batteries WithElectroactive Nanoparticles,” incorporated herein by reference.Similarly, submicron/nanoscale particles have the capability ofachieving high rates of discharge. Other advantageoussubmicron/nanoscale powders of metal compositions, of which a largenumber are described further below, that can incorporate lithium intotheir lattices can be formed for use in anodes and/or cathodes, asdescribed herein.

Other compositions for submicron/nanoscale particles can be selected toyield advantageous properties for electronic applications. For example,electrically conductive particles can advantageously used to formelectrical interconnects within electronic structures, such asintegrated electrical circuits or electro-optical circuits. Similarly,silicon particles, germanium particles, or gallium arsenide particlescan be formed for the introduction of semiconductor materials. Othermaterials introduce high electrical capacitance capabilities due totheir dielectric properties, such as BaTiO₃ and Ta.

Particle Synthesis within a Reactant Flow

Laser pyrolysis has been demonstrated to be a valuable tool for theproduction of submicron/nanoscale particles with a wide range ofparticle compositions and structures alone or with additionalprocessing. Using light reactive deposition, the particles can bedeposited onto a substrate as a coating. The reactant deliveryapproaches described in detail below can be adapted for producingparticles and/or coatings in flowing reactant systems, with or without aradiation, e.g., a light source. In some embodiments, other chemicalreaction synthesis methods, as discussed above, using a flowing reactantstream, as well as other chemical synthesis methods, can be adapted forproducing desired particles and/or coatings. Laser pyrolysis is aparticularly appropriate approach in some applications for producing adoped particles and/or complex particle compositions because laserpyrolysis can produce highly uniform product particles at highproduction/deposition rates.

Flowing reactant systems generally comprise a reactant deliveryapparatus that directs a flow through a reaction chamber. The reactionof the reactant flow takes place in the reaction chamber. The reactionzone may or may not be localized in a narrow region within the reactionchamber. The use of a radiation, e.g., light, beam, to drive thereaction can result in a localized reaction zone that leads to highuniformity of the particles. Beyond the reaction zone, the flowcomprises product particles, unreacted reactants, reaction by-productsand inert gases. The flow can continue to a collector and/or adeposition surface at which at least a portion of the product particlesare harvested from the flow. Continuous supply of reactants to the flowand removal of product particles from the flow during the course of thereaction characterizes the reaction process within the flowing reactantsystem.

Light reactive deposition can incorporate some of the particleproduction features of laser pyrolysis for the production of coatings.In particular, the versatility of forming particles with a range ofparticle compositions and structures can be adapted for the formation ofparticle coatings by light reactive deposition with a comparable rangein particle compositions. In general, product particles within a flowingreactant system can be deposited onto a substrate as a coating withinthe reaction chamber, or directed to a separate coating chamber fordeposition onto a substrate, or directed to a collector for collectionas a powder.

Laser pyrolysis has become the standard terminology for flowing chemicalreactions driven by an intense radiation, e.g., light, with rapidquenching of product after leaving a narrow reaction region defined bythe radiation. The name, however, is a misnomer in the sense thatradiation from non-laser sources, such as a strong, incoherent light orother radiation beam, can replace the laser. Also, the reaction is not apyrolysis in the sense of a thermal pyrolysis. The laser pyrolysisreaction is not solely thermally driven by the exothermic combustion ofthe reactants. In fact, in some embodiments, laser pyrolysis reactionscan be conducted under conditions where no visible light emissions areobserved from the reaction, in stark contrast with pyrolytic flames.Thus, as used herein, laser pyrolysis refers generally to aradiation-driven flowing reaction. Light reactive deposition involvescomparable processes as laser pyrolysis for the particle production,although some characteristics of the flow may be altered to accommodatethe coating process.

The reaction conditions can determine the qualities of the particlesproduced by laser pyrolysis. The reaction conditions for laser pyrolysiscan be controlled relatively precisely in order to produce particleswith desired properties. For example, the reaction chamber pressure,flow rates, composition and concentration of reactants, radiationintensity, radiation energy/wavelength, type and concentration of inertdiluent gas or gases in the reaction stream, temperature of the reactantflow can affect the composition and other properties of the productparticles, for example, by altering the time of flight of thereactants/products in the reaction zone and the quench rate. Thus, in aparticular embodiment, one or more of the specific reaction conditionscan be controlled. The appropriate reaction conditions to produce acertain type of particles generally depend on the design of theparticular apparatus. Specific conditions used to produce selectedparticles in particular apparatuses are described below in the Examples.Furthermore, some general observations on the relationship betweenreaction conditions and the resulting particles can be made.

Increasing the light power results in increased reaction temperatures inthe reaction region as well as a faster quenching rate. A rapidquenching rate tends to favor production of higher energy phases, whichmay not be obtained with processes near thermal equilibrium. Similarly,increasing the chamber pressure also tends to favor the production ofhigher energy phases. Also, increasing the concentration of the reactantserving as the oxygen source or other secondary reactant source in thereactant stream favors the production of particles with increasedamounts of oxygen or other secondary reactant.

Reactant velocity of the reactant gas stream is inversely related toparticle size so that increasing the reactant velocity tends to resultin smaller particle sizes. A significant factor in determining particlesize is the concentration of product composition condensing into productparticles. Reducing the concentration of condensing product compositionsgenerally reduces the particle size. The concentration of condensingproduct can be controlled by dilution with non-condensing, e.g., inert,compositions or by changing the pressure with a fixed ratio ofcondensing product to non-condensing compositions, with a reduction inpressure generally leading to reduced concentration and a correspondingreduction in particle size and vice versa, or by combinations thereof,or by any other suitable means.

Light power also influences particle size with increased light powerfavoring larger particle formation for lower melting temperaturematerials and smaller particle formation for higher melting temperaturematerials. Also, the growth dynamics of the particles have a significantinfluence on the size of the resulting particles. In other words,different forms of a product composition have a tendency to formdifferent size particles from other phases under relatively similarconditions. Similarly, under conditions at which populations ofparticles with different compositions are formed, each population ofparticles generally has its own characteristic narrow distribution ofparticle sizes.

Materials of interest include amorphous materials, crystalline materialsand combinations thereof. Amorphous materials possess short-range orderthat can be very similar to that found in crystalline materials. Incrystalline materials, the short-range order comprises the buildingblocks of the long-range order that distinguishes crystalline andamorphous materials. In other words, translational symmetry of theshort-range order building blocks found in amorphous materials createslong-range order that defines a crystalline lattice. For example, silicaglass is an amorphous material comprised of (SiO₄)⁴⁻ tetrahedra that arebonded together at irregular bond angles. The regularity of thetetrahedra provides short-range order but the irregularity of the bondangles prevents long-range order. In contrast, quartz is a crystallinesilica material comprised of the same (SiO₄)⁴⁻ tetrahedra that arebonded together at regular bond angles to form long-range order whichresults in a crystalline lattice. In general, the crystalline form is alower energy state than the analogous amorphous form. This provides adriving force towards formation of long-range order. In other words,given sufficient atomic mobility and time, long-range order can form.

In laser pyrolysis, a wide range of inorganic materials can be formed inthe reactive process. Based on kinetic principles, higher quench ratesfavor amorphous particle formation while slower quench rates favorcrystalline particle formation as there is time for long-range order todevelop. Faster quenches can be accomplished with a faster reactantstream velocity through the reaction zone. In addition, some precursorsmay favor the production of amorphous particles while other precursorsfavor the production of crystalline particles of similar or equivalentstoichiometry. Low laser power can also favor formation of amorphousparticles. Specifically, amorphous particles can beconsolidated/densified under appropriate conditions to form amorphouslayers, such as optical glasses. Amorphous particles are more easilyconsolidated into a glass layer since amorphous particles do not have along-range order that is disrupted to form a glass layer. The formationof amorphous oxides is described further in U.S. Pat. No. 6,106,798 toKambe et al., entitled “Vanadium Oxide Nanoparticles,” incorporatedherein by reference. Also, crystalline materials are of interest foroptical and/or other applications. Crystalline particles can beconsolidated into single crystalline or polycrystalline materials. Whileit may be easier to consolidate amorphous particles into glasses andcrystalline particles into crystalline layers, crystalline particles canbe consolidated into amorphous layers under appropriate consolidationconditions such as heating the particles to a temperature above themelting temperature followed by quenching at a rate that preventslong-range order formation. Amorphous particles can be consolidated intocrystalline layers under appropriate consolidation conditions includingthe heating and cooling at rates that provide time for long-range orderto develop.

To form a desired composition in the reaction process, one or moreprecursors supply the one or more metal/metalloid elements that form thedesired composition. The reactant stream generally would include thedesired metal and, additionally or alternatively, metalloid elements toform the host material and, optionally, dopant(s)/additive(s) inappropriate proportions to produce product particles with a desiredcomposition. The composition of the reactant stream can be adjustedalong with the reaction condition(s) to generate desired productparticles with respect to composition and structure. Based on theparticular reactants and reaction conditions, the product particles maynot have the same proportions of metal/metalloid elements as thereactant stream since the elements may have different efficiencies ofincorporation into the particles, i.e., yields with respect to unreactedmaterials. The designs of the reactant nozzles for radiation drivenreactions described herein are designed for high yields with highreactant flows. Furthermore, additional appropriate precursor(s) cansupply any desired dopant/additive element(s).

Metalloids are elements that exhibit chemical properties intermediatebetween or inclusive of metals and nonmetals. Metalloid elementscomprise silicon, boron, arsenic, antimony, and tellurium. Whilephosphorous is located in the periodic table near the metal elements, itis not generally considered a metalloid element. However, phosphorous inthe form of P₂O₅ is a composition of interest. For convenience, as usedherein including in the claims, phosphorous is also considered ametalloid element. Astatine perhaps can be considered a metalloid also,but it is highly radioactive with the longest lived isotopes having ahalf life of about 8 hours. Elements from the groups Ib, IIb, IIIb, IVb,Vb, VIb, VIII) and VIIIb are referred to as transition metals. Inaddition to the alkali metals of group I, the alkali earth metals ofgroup II and the transition metals, other metals include, for example,aluminum, gallium, indium, thallium, germanium, tin, lead, bismuth andpolonium. The non-metal/metalloid elements include hydrogen, the noblegases, carbon, nitrogen, oxygen, fluorine, sulfur, chlorine, selenium,bromine, and iodine. Inorganic compositions broadly covercompositions/materials without carbon-carbon chains defining thechemical structures of the compositions. Thus, carbon solids dominatedby carbon networks, for example, fullerenes, carbon black, graphite andthe like, rather than carbon-carbon chains are also considered inorganicmaterials.

Laser pyrolysis has been performed generally with gas/vapor phasereactants. Many precursor compositions, such as metal/metalloidprecursor compositions, can be delivered into the reaction chamber as agas. Appropriate precursor compositions for gaseous delivery generallyinclude compositions with reasonable vapor pressures, i.e., vaporpressures sufficient to get desired amounts of precursor gas/vapor intothe reactant stream. The vessel holding liquid or solid precursorcompositions can be heated (cooled) to increase (decrease) the vaporpressure of the precursor, if desired. Solid precursors generally areheated to produce a sufficient vapor pressure. A carrier gas can bebubbled through a liquid precursor to facilitate delivery of a desiredamount of precursor vapor. Similarly, a carrier gas can be passed overthe solid precursor to facilitate delivery of the precursor vapor.Alternatively or additionally, a liquid precursor can be directed to aflash evaporator to supply a composition at a selected vapor pressure.

The use of exclusively gas phase reactants can be challenging withrespect to the types of precursor compositions that can be usedconveniently. Thus, techniques have been developed to introduce aerosolscontaining precursors, such as metal/metalloid precursors, into laserpyrolysis chambers. Improved aerosol delivery apparatuses for flowingreaction systems are described further in U.S. Pat. No. 6,193,936 toGardner et al., entitled “Reactant Delivery Apparatuses,” incorporatedherein by reference.

Using aerosol delivery apparatuses, solid precursor compositions can bedelivered by dissolving the compositions in a solvent. Alternatively,powdered precursor compositions can be dispersed in a liquid/solvent foraerosol delivery. Liquid precursor compositions can be delivered as anaerosol from a neat liquid, a multiple liquid dispersion or a liquidsolution. Aerosol reactants can be used to obtain a significant reactantthroughput. A solvent/dispersant can be selected to achieve desiredproperties of the resulting solution/dispersion. Suitablesolvents/dispersants include water, methanol, ethanol, isopropylalcohol, other organic solvents and mixtures thereof. The solvent shouldhave a desired level of purity such that the resulting particles have adesired purity level. Some solvents, such as isopropyl alcohol, aresignificant absorbers of infrared light from a CO₂ laser such that noadditional light absorbing composition may be needed within the reactantstream if a CO₂ laser is used as a light source.

If precursors are delivered as an aerosol with a solvent present, thesolvent generally can be rapidly evaporated by the radiation (e.g.,light) beam in the reaction chamber such that a gas phase reaction cantake place. The resulting particles are not generally highly porous, incontrast to other approaches based on aerosols in which the solventcannot be driven off rapidly. Thus, the fundamental features of thelaser pyrolysis reaction can be unchanged by the presence of an aerosol.Nevertheless, the reaction conditions are affected by the presence ofthe aerosol. Below in the Examples, conditions are described for theproduction of submicron/nanoscale particles using aerosol precursors inlaser pyrolysis reaction chambers. Thus, the parameters associated withaerosol reactant delivery can be explored further based on thedescription below.

The precursor compositions for aerosol delivery are dissolved in asolution generally with a concentration in the range(s) greater thanabout 0.1 molar. Generally, increasing the concentration of precursor inthe solution increases the throughput of reactant through the reactionchamber. As the concentration increases, however, the solution canbecome more viscous such that the aerosol may have droplets with largersizes than desired. Thus, selection of solution concentration caninvolve a balance of factors in the selection of a suitable solutionconcentration.

For embodiments involving a plurality of metal/metalloid elements, themetal/metalloid elements can be delivered all as vapor, all as aerosolor as any combination thereof. If a plurality of metal/metalloidelements is delivered as an aerosol, the precursors can bedissolved/dispersed within a single solvent/dispersant for delivery intothe reactant flow as a single aerosol. Alternatively, the plurality ofmetal/metalloid elements can be delivered within a plurality ofsolutions/dispersions that are separately formed into an aerosol. Thegeneration of a plurality of aerosols can be helpful if convenientprecursors are not readily soluble/dispersible in a commonsolvent/dispersant. The plurality of aerosols can be introduced into acommon gas flow for delivery into the reaction chamber through a commonnozzle. Alternatively, a plurality of reactant inlets can be used forthe separate delivery of aerosol and/or vapor reactants into thereaction chamber such that the reactants mix within the reaction chamberprior to entry into the reaction zone. Exemplary reactant deliveryapparatuses are described further below.

In addition, for the production of highly pure materials, it may bedesirable to use a combination of vapor and aerosol reactants. Vapor/gasreactants generally can be supplied at higher purity than is generallyavailable at reasonable cost for aerosol delivered compositions. Thiscan be particular convenient for the formation of doped optical glasses.For example, very pure silicon can be delivered in an easily vaporizableform, such as silicon tetrachloride. At the same time, some elements,especially rare earth dopant(s)/additive(s), cannot be convenientlydelivered in vapor form. Thus, in some embodiments, a majority of thematerial for the product compositions can be delivered in vapor/gas formwhile other elements are delivered in the form of an aerosol. The vaporand aerosol can be combined for reaction, among other ways, followingdelivery through a single reactant inlet or a plurality of inlets.

The particles, in some embodiments, further comprise one or morenon-(metal/metalloid) elements. For example, several compositions ofinterest are oxides. Thus, an oxygen source should also be present inthe reactant stream. The oxygen source can be the metal/metalloidprecursor itself if it comprises one or more oxygen atoms or a secondaryreactant can supply the oxygen. The conditions in the reactor should besufficiently oxidizing to produce the oxide materials.

In particular, secondary reactants can be used in some embodiments toalter the oxidizing/reducing conditions within the reaction chamberand/or to contribute non-metal/metalloid elements or a portion thereofto the reaction products. Suitable secondary reactants serving as anoxygen source include, for example, O₂, CO, H₂O, CO₂, O₃ and the likeand mixtures thereof. Molecular oxygen can be supplied as air. In someembodiments, the metal/metalloid precursor compositions comprise oxygensuch that all or a portion of the oxygen in product particles iscontributed by the metal/metalloid precursors. Similarly, liquids usedas a solvent/dispersant for aerosol delivery can similarly contributesecondary reactants, e.g., oxygen, to the reaction. In other words, ifone or more metal/metalloid precursors comprise oxygen and/or if asolvent/dispersant comprises oxygen, a separate secondary reactant,e.g., a vapor reactant, may not be needed to supply oxygen for productparticles. Other secondary reactants of interest are described below.

In one embodiment, a secondary reactant composition should not reactsignificantly with the metal/metalloid precursor(s) prior to enteringthe radiation reaction zone since this can result in the formation oflarger particles and/or damage the inlet nozzle. Similarly, if aplurality of metal/metalloid precursors is used, these precursors shouldnot significantly react prior to entering the radiation reaction zone.If the reactants are spontaneously reactive, a metal/metalloid precursorand the secondary reactant and/or different metal/metalloid precursorscan be delivered in separate reactant inlets into the reaction chambersuch that they are combined just prior to reaching the light beam.

Laser pyrolysis can be performed with radiation at a variety of opticalfrequencies, using either a laser or other intense light source.Convenient light sources operate in the infrared portion of theelectromagnetic spectrum, although other wavelengths can be used, suchas the visible and infrared regions of the spectrum. Excimer lasers canbe used as ultraviolet sources. CO₂ lasers are particularly usefulsources of infrared light. Infrared absorber(s) for inclusion in thereactant stream include, for example, C₂H₄, isopropyl alcohol, NH₃, SF₆,SiH₄ and O₃. O₃ can act as both an infrared absorber and as an oxygensource. The radiation absorber(s), such as the infrared absorber(s), canabsorb energy from the radiation beam and distribute the energy to theother reactants to drive the pyrolysis.

Generally, the energy absorbed from the radiation beam, e.g., lightbeam, increases the temperature at a tremendous rate, many times therate that heat generally would be produced by exothermic reactions undercontrolled condition(s). While the process generally involvesnonequilibrium conditions, the temperature can be describedapproximately based on the energy in the absorbing region. The laserpyrolysis process is qualitatively different from the process in acombustion reactor where an energy source initiates a reaction, but thereaction is driven by energy given off by an exothermic reaction. Thus,while the light driven process is referred to as laser pyrolysis, it isnot a traditional pyrolysis since the reaction is not driven by energygiven off by the reaction but by energy absorbed from a radiation beam.In particular, spontaneous reaction of the reactants generally does notproceed significantly, if at all, back down the reactant flow toward thenozzle from the intersection of the radiation beam with the reactantstream. If necessary, the flow can be modified such that the reactionzone remains confined as desired.

An inert shielding gas can be used to reduce the amount of reactant andproduct molecules contacting the reactant chamber components. Inertgases can also be introduced into the reactant stream as a carrier gasand/or as a reaction moderator. Appropriate inert gases generallyinclude, for example, Ar, He and N₂.

The particle production rate based on improved reactant deliveryconfigurations described below can yield particle production rates inthe range(s) of at least about 50 g/h, in other embodiments in therange(s) of at least about 100 g/h, in further embodiments in therange(s) of at least about 250 g/h, in additional embodiments in therange(s) of at least about 1 kilogram per hour (kg/h) and in general upin the range(s) up to at least about 10 kg/h. In general, these highproduction rates can be achieved while obtaining relatively highreaction yields, as evaluated by the portion of metal/metalloid nucleiin the flow that are incorporated into the product particles. Ingeneral, the yield can be in the range(s) of at least about 30 percentbased on the limiting reactant, in other embodiments in the range(s) ofat least about 50 percent, in further embodiments in the range(s) of atleast about 65 percent, in other embodiments in the range(s) of at leastabout 80 percent and in additional embodiments in the range(s) of atleast about 95 percent based on the metal/metalloid nuclei in thereactant flow. A person of ordinary skill in the art will recognize thatadditional values of particle production rate and yield within thesespecific values are contemplated and are within the present disclosure.

Compositions of Particles and Coatings

A variety of particles can be produced by laser pyrolysis. Adaptation oflaser pyrolysis for the performance of light reactive deposition can beused to produce coatings of comparable compositions as the particleswith selected compositions that can be produced by laser pyrolysis.Specifically, the compositions can include one or more metal/metalloidelements forming a crystalline or amorphous material with an optionaldopant or additive composition. In addition, dopant(s)/additive(s) canbe used to alter the optical, chemical and/or physical properties of theparticles. Generally, the powders comprise fine or ultrafine particleswith particle sizes in the submicron/nanometer range. The particles mayor may not partly fuse or sinter during the deposition while forming apowder coating. To form a densified layer, a powder coating can beconsolidated. Incorporation of the dopant(s)/additive(s) into the powdercoating, during its formation or following its formation, results in adistribution of the dopant(s)/additive(s) through the densifiedmaterial.

In general, the submicron/nanoscale particles, as a particle collectionor a powder coating, can generally be characterized as comprising acomposition including a number of different elements and present invarying relative proportions, where the number and the relativeproportions can be selected as a function of the application for theparticles. Typical numbers of different elements include, for example,numbers in the range(s) from about 2 elements to about 15 elements, withnumbers of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 beingcontemplated, in which some or all of the elements can bemetal/metalloid element. General numbers of relative proportionsinclude, for example, values in the range(s) from about 1 to about1,000,000, with numbers of about 1, 10, 100, 1000, 10000, 100000,1000000, and suitable sums thereof being contemplated. In addition,elemental materials are contemplated in which the element is in itselemental, un-ionized form, such as a metal/metalloid element, i.e., M⁰.

Alternatively or additionally, such submicron/nanoscale particles can becharacterized as having the following formula:

A_(a)B_(b)C_(c)D_(d)E_(e)F_(f)G_(g)H_(h)I_(i)J_(i)K_(k)L_(i)M_(m)N_(n)O_(o),

where each A, B, C, D, E, F, G, H, I, J, K, L, M, N, and O isindependently present or absent and at least one of A, B, C, D, E, F, G,H, I, J, K, L, M, N, and O is present and is independently selected fromthe group consisting of elements of the periodic table of elementscomprising Group 1A elements, Group 2A elements, Group 3B elements(including the lanthanide family of elements and the actinide family ofelements), Group 4B elements, Group 5B elements, Group 6B elements,Group 7B elements, Group 8B elements, Group 1B elements, Group 2Belements, Group 3A elements, Group 4A elements, Group 5A elements, Group6A elements, and Group 7A elements; and each a, b, c, d, e, f, g, h, i,j, k, l, m, n, and o is independently selected and stoichiometricallyfeasible from a value in the range(s) from about 1 to about 1,000,000,with numbers of about 1, 10, 100, 1000, 10000, 100000, 1000000, andsuitable sums thereof being contemplated. The materials can becrystalline, amorphous or combinations thereof. In other words, theelements can be any element from the periodic table other than the noblegases. As described herein, all inorganic compositions are contemplated,as well as all subsets of inorganic compounds as distinct inventivegroupings, such as all inorganic compounds or combinations thereofexcept for any particular composition, group of compositions, genus,subgenus, alone or together and the like.

While some compositions are described with respect to particularstoichiometries/compositions, stoichiometries generally are onlyapproximate quantities. In particular, materials can have contaminants,defects and the like. Similarly, some amorphous materials can compriseessentially blends such that the relative amounts of differentcomponents are continuously adjustable over ranges in which thematerials are miscible. In other embodiments, phase separated amorphousmaterials can be formed with differing compositions at different domainsdue to immiscibility of the materials at the average composition.Furthermore, for amorphous and crystalline materials in whichmetal/metalloid compounds have a plurality of oxidation states, thematerials can comprise a plurality of oxidation states. Thus, whenstoichiometries are described herein, the actual materials may compriseother stoichiometries of the same elements also, such as SiO₂ alsoinclude some SiO and the like.

In some embodiments, such as for optical materials, powders comprise asa host material, for example, silicon particles, metal particles, andmetal/metalloid compositions, such as, metal/metalloid oxides,metal/metalloid carbides, metal/metalloid nitrides, metal/metalloidphosphides, metal/metalloid sulfides, metal/metalloid tellurides,metal/metalloid selenides, metal/metalloid arsinides and mixtures andcombinations thereof. Especially in amorphous materials, great varietiesof elemental compositions are possible within a particular material.While laser pyrolysis is versatile with respect to the production ofparticles, with a wide range of compositions, in one embodiment, certainhost materials for the introduction of dopant(s)/additive(s) aredesirable because of their particular ability to be processed into glasslayers and/or their desirability for optical materials that areprocessable into optical devices. For optical materials, some materialsof particular interest comprise, for example, silicon oxide (silica),phosphate glasses, germanium oxide, aluminum oxide, indium phosphide,lithium niobate, lithium tantalate, telluride glasses, aluminum oxide,titanium oxide, gallium arsenide, combinations thereof and dopedversions thereof. Some metal/metalloid oxides are particularly desirablefor optical applications and/or for their ability to consolidate intouniform glass layers. Suitable glass forming host oxides for dopinginclude, for example, TiO₂, SiO₂, GeO₂, Al₂O₃, P₂O₅, B₂O₃, TeO₂,CaO—Al₂O₃, V₂O₅, BiO₂, Sb₂O₅ and combinations and mixtures thereof.Other metal/metalloid oxides have desirable optical properties incrystalline form, such as LiNbO₃, LiTaO₃, Y₃Al₅O₁₂ (YAG) and rare earth,especially Nd, doped YAG. The approaches described herein for particleformation and coating formation are particularly suitable for formationof metal/metalloid oxide particles with or withoutdopant(s)/additive(s). Similarly, laser pyrolysis and light reactivedeposition are suitable approaches for producing particle collectionsand powder coatings for the non-oxide materials, as described furtherbelow.

In addition, particles and powder coatings can include one or moredopants/additives within an amorphous material and/or a crystallinematerial. Dopant(s)/additive(s), which can be complex blends ofdopant/additive composition(s), generally are included innon-stoichiometric amounts. A dopant/additive is generally metal ormetalloid element, although other dopant(s)/additive(s) of interestinclude fluorine, chlorine, nitrogen and/or carbon, which substitute foroxygen in oxides or other anions relative to metal/metalloid components.Since these anion dopant(s)/additive(s), like some cation dopants, tendto disrupt the oxygen bonded network of oxides, these tend to lower theflow temperature of oxide glasses, and these dopant(s)/additive(s) tendto lower the index-of-refraction and the dielectric constant. Thedopant(s)/additive(s) generally can replace other constituents withinthe material in order to maintain overall electrical neutrality.Dopant(s)/additive(s) can impart desirable properties to the resultingmaterials. The amount of dopant(s)/additive(s) can be selected to yielddesired properties while maintaining appropriate chemical stability tothe material. In crystalline materials, dopant/additive element(s) canreplace host elements at lattice sites, dopant/additive element(s) canreside at previously unoccupied lattice sites and/or dopant/additiveelement(s) can be located at interstitial sites. Unlikedopant(s)/additive(s) within crystalline materials in which the crystalstructure influences incorporation of the dopant(s)/additive(s),dopant(s)/additive(s) within amorphous materials can behave more as acomposition dissolved within the host material to form a solid mixture.Thus, the overall composition of the material influences the chemicalproperties, including the processing parameters and stability, of theresulting combined materials. Solubility of dopant(s)/additive(s) withina host amorphous material can influence the amount of a particulardopant/additive that can be homogeneously integrated into a consolidatedglass.

A dopant, such as a rare earth dopant, generally comprises in therange(s) less than about 15 mole percent of the metal/metalloid in thecomposition, in further embodiments in the range(s) less than about 10mole percent, in some embodiments in the range(s) from about 0.001 molepercent to about 5 mole percent, and in other embodiments in therange(s) from about 0.025 to about 1 mole percent of the metal/metalloidin the composition. A person of ordinary skill in the art will recognizethat the present disclosure similarly covers ranges within thesespecific ranges. Additive compositions are similar to dopantcompositions except that they generally are included at higher amountswhile still being a minority component of the composition, i.e., in therange(s) less than about 50 mole percent of the composition. Foramorphous materials, additive(s) can be modifiers or intermediatecompositions between glass formers and modifiers. Modifiers can disruptthe oxygen network within an oxide glass to modify the glass properties,such as flow temperature, coefficient of thermal expansion, chemicaldurability and the index-of-refraction. Thus, additive(s) can be usefulfor many of the same purposes as dopant(s). Doped and doping, forconvenience, can refer to materials with dopants and/or additives andthe process of incorporating dopants and/or additives, respectively.Suitable dopant(s)/additive(s) include, for example, rare earth metalsamong other suitable metal/metalloid element. Rare earth dopants canimpart desirable modifications of properties, such asindex-of-refraction, photosensitivity, fluorescence and paramagnetism.

Powders and coatings, e.g., glass layers, can be formed with complexcompositions including, for example, one or more metal/metalloidelements in a host material and, optionally, one or more selecteddopants/additives in the amorphous host material. Similarly, crystallinematerials can be formed with dopant(s)/additive(s) within a crystallinehost material. The doped materials can be formed by directly depositingparticles to form a powder coating using light reactive deposition andsubsequently consolidating the powder coating into a uniform layer of aglass, polycrystalline or crystalline material. Alternatively, anydopant(s)/additive(s) can be introduced to a powder coating followingits formation for incorporation into a consolidated uniform material, asdescribed further below.

Submicron/nanoscale particles can be produced with complex compositionsusing laser pyrolysis and light reactive deposition. Materials can beformed with desired compositions by appropriately introducing a reactantcomposition to form the desired host material. The elements that modifythe composition, such as elements introduced in approximatelystoichiometric amounts as well as dopant(s)/additive(s), can beintroduced into an appropriate host material, which can be particlecollections or powder coatings, either during the formation of the hostmaterial or subsequent to formation of the particles/powder coating.Specifically, selected elements can be introduced at desired amounts byvarying the composition of the reactant stream. The conditions in thereactor can also be selected to produce the desired materials. Inalternative embodiments, a modifying element is applied to an alreadyformed particle collection or powder coating in proportion to thedesired levels for the ultimate composition. Upon heat treatment, thedesired composition is formed. Heat treatments to introduce modifyingelements are described further below.

With respect to glasses, while a variety of materials are of interest,silica (SiO₂)-based glasses are of interest due to their existingcommercial applications. Other glass forming materials that are suitablefor combining with silica to form amorphous host materials include, forexample, Al₂O₃, Na₂O, B₂O₃, P₂O₃, GeO₂, and the like and combinationsthereof. Thus, a plurality of glass forming compositions can be combinedto form a blended glass host composition with desired properties, suchas index-of-refraction and glass transition temperature. The blendedglass host materials can be doped with further materials to furtheradjust the properties of the material.

A wide range of silica glass compositions have significant opticalapplications or potential optical applications. Generally, these silicaglasses can be formed by light reactive deposition based on thedescription herein. The silica glass generally is combined with otherglass forming compositions to alter the optical properties, such asindex-of-refraction, and or alter the processing properties, such aslowering the flow temperature. Some representative compositions withsuitable optical properties are summarized below.

Aluminosilicate glasses form a group of compositions with useful opticalapplications. This group comprises compositions in mole percents ofinterest about 70% SiO₂, about 30% Al₂O₃ and about 0.025% Er₂O₃; about93.5% SiO₂, about 5.6% Al₂O₃ and about 0.9% Er₂O₃; and, about 58% SiO₂,about 23% Al₂O₃, about 19% Tb₂O₃ and about 0.4% Sb₂O₃. Sodiumaluminosilicates are described further in the example, and can comprisea composition in mole percent about 59% SiO₂, about 20% Al₂O₃, about 20%Na₂O and about 1% Er₂O₃. A representative soda-lime silicate has acomposition in mole percent of about 70% SiO₂, about 15% CaO, about 15%Na₂O and about 0.03% CrO₂. Control of oxygen partial pressure duringconsolidation can be used to oxidize Cr⁺² (CrCl₂) and/or Cr⁺³ (Cr(NO₃)₃)to Cr⁺⁴. A representative silica can be doped with chromium, about 0.05%CrO₂. Another example is phosphosilicate glasses, exemplified by acomposition comprising about 88% SiO₂, about 11% P₂O₃ and about 0.8%Er₂O₃, in mole percent.

Some non-silica glasses are also very suitable for optical applications,such as germinates, phosphates, aluminocalcinates and tellurides.Representative germanate glasses in mole percent comprise a firstcomposition of about 80% GeO₂, about 20% SiO₂ and about 0.5% Er₂O₃; asecond composition of about 72% GeO₂, about 18% SiO₂, about 10% Al₂O₃,about 0.5% Er₂O₃ and about 0.5 Yb₂O₃; a third composition of about 72%GeO₂, about 18% SiO₂, about 10% P₂O₅, about 0.5% Er₂O₃ and about 0.5Yb₂O₃; or a fourth composition of about 60% GeO₂, about 24% K₂O, about16% Ga₂O₃ and about 0.1% Tm₂O₃. Two representative phosphate glassescomprise compositions in mole percents of about 58% P₂O₅, about 23%Na₂O, about 13% Al₂O₃ and about 6% Er₂O₃; and, about 50% P₂O₅, about 17%Na₂O, about 30% SiO₂ and about 3% Er₂O₃. Some representativealuminocalcinates comprise compositions in mole percent in the range(s)of about 57.75% to about 59.55% CaO, about 23% to about 28% Al₂O₃, about4% to about 8% MgO, about 7% to about 8.5% SiO₂, about 0 to about 1%Er₂O₃ and about 0 to about 1% Yb₂O₃. Two representative tellurideglasses comprise a composition in mole percent of about 75% TeO₂, about20% ZnO, about 5% Na₂O, and about 0.15% Er₂O₃; or a composition in molepercent of about 80% TeO₂, about 10% ZnO, about 10% Na₂O, about 1%(Er₂O₃, Tm₂O₃ or Nd₂O₃).

Some crystalline materials also have desirable optical properties. Somerepresentative crystalline optical materials comprise compositions inmole percent of about 97% Al₂O₃ and about 3% Er₂O₃; about 90% Al₂O₃,about 10% (Er₂O₃, Nd₂O₃ or Tb₂O₃); about 99.3% TiO₂ and about 0.75%Er₂O₃; and, about 96.7% YVO₄, about 3% Yb₂O₃ and about 0.3% Er₂O₃.

Dopant(s)/additive(s) can be introduced to vary properties, such asoptical properties and physical properties, of the particles and/or aresulting layer of particles with or without consolidation. For example,dopant(s)/additive(s) can be introduced to change theindex-of-refraction of the material. For optical applications, theindex-of-refraction can be varied to form specific optical devices thatoperate with light of a selected frequency range. Dopant(s)/additive(s)can also be introduced to alter the processing properties of thematerial. In particular, some dopant(s)/additive(s) change the flowtemperature, i.e., the glass transition temperature, such that the glasscan be processed at lower temperatures. Dopants/additives can alsointeract within the materials. For example, some dopant(s)/additive(s),such as P₂O₅ and Al₂O₃, are introduced to increase the solubility ofother dopant(s)/additive(s). Doped materials are useful in theproduction of optical devices. Using the techniques described herein,the doped materials can be formulated into planar optical devices.

In one aspect, particles of interest comprise amorphous compositionsthat form optical glasses with a plurality of dopants/additives. In someembodiments, the one or plurality of dopants/additives comprise rareearth metals. Rare earth metals are particularly desirable because oftheir modification of optical properties of the materials. If theparticles are consolidated into a substantially uniform layer, theresulting material can have an index-of-refraction influenced by therare earth dopant(s)/additive(s) as well as other dopant(s)/additive(s).In addition, the rare earth dopant(s)/additive(s) can influence theoptical emission properties that can alter the application of thematerials for the production of optical amplifiers and other opticaldevices. Rare earth metals comprise the transition metals of the groupIIIb of the periodic table. Specifically, the rare earth elementscomprise Sc, Y and the Lanthanide series. Other suitabledopant(s)/additive(s) include elements of the actinide series. Foroptical glasses, the rare earth metals of interest as dopants/additivescomprise Er, Yb, Nd, La, Ce, Tb, Dy, Ho, Sm, Eu, Gd, Pr, Tm, Sc, Y, andthe like and combinations thereof. Suitable non-rare earth metaldopants/additives include, for example, Al, Ga, Mg, Sr, Zn, Bi, Sb, Zr,Pb, Li, Na, K, Ba, W, Si, Ge, P, B, Te, Ca, Rb, Sn, In, Ti, Au, Ag, Ta,Mo, Nb, and the like and combinations thereof. Also, certain first-rowtransition metals have optical emission properties in the visible orinfrared regions of the spectrum. Suitable first-row transition elementhaving desirable optical properties as dopants/additives include, forexample, V, Cr, Mn, Fe, Co, Ni and Cu. the wavelength of the opticalemission depends on the oxidation-state of the transition-metal. Thisoxidation state generally can be controlled by adjusting the oxygenpartial-pressure during the consolidation process.

Various materials have been formed as submicron/nanoscale particlesusing laser pyrolysis. Some of these materials are described in thefollowing description. Using light reactive deposition, these materialscan be formed directly as coatings in the form of powder coatings. Basedon the description and examples herein, a range of additional materialscan be produced by laser pyrolysis and light reactive deposition.Specifically, suitable approaches for the formation of some improvedmaterials are outlined below.

For example, the production of silicon oxide submicron/nanoscaleparticles is described in copending and commonly assigned U.S. patentapplication Ser. No. 09/085,514, now U.S. Pat. No. 6,726,990 to Kumar etal., entitled “Silicon Oxide Particles,” incorporated herein byreference. This patent application describes the production of amorphousSiO₂. The production of titanium oxide submicron/nanoscale particles andcrystalline silicon dioxide submicron/nanoscale particles is describedin U.S. Pat. No. 6,387,531 to Bi et al., entitled “Metal (Silicon)Oxide/Carbon Composites,” incorporated herein by reference. Inparticular, this application describes the production of anatase andrutile TiO₂.

In addition, submicron/nanoscale manganese oxide particles have beenformed. The production of these particles is described in copending andcommonly assigned U.S. patent application Ser. No. 09/188,770, now U.S.Pat. No. 6,506,493 to Kumar et al., entitled “Metal Oxide Particles,”incorporated herein by reference. This application describes theproduction of MnO, Mn₂O₃, Mn₃O₄ and Mn₅O₈.

Also, the production of vanadium oxide submicron/nanoscale particles isdescribed in U.S. Pat. No. 6,106,798 to Bi et al., entitled “VanadiumOxide Nanoparticles,” incorporated herein by reference. Similarly,silver vanadium oxide submicron/nanoscale particles have been produced,as described in U.S. Pat. No. 6,225,007 to Home et al., and U.S. Pat.No. 6,394,494 to Reitz et al., both entitled “Metal Vanadium OxideParticles,” and 09/649,752, now U.S. Pat. No. 6,503,646 to Ghantous etal., entitled “High Rate Batteries,” all three of which are incorporatedherein by reference.

Furthermore, lithium manganese oxide submicron/nanoscale particles havebeen produced by laser pyrolysis along with or without subsequent heatprocessing, as described in copending and commonly assigned U.S. patentapplication Ser. No. 09/188,768, now U.S. Pat. No. 6,607,706 to Kumar etal., entitled “Composite Metal Oxide Particles,” and 09/334,203, nowU.S. Pat. No. 6,482,374 to Kumar et al., entitled “Reaction Methods forProducing Ternary Particles,” and U.S. Pat. No. 6,136,287 to Home etal., entitled “Lithium Manganese Oxides and Batteries,” all three ofwhich are incorporated herein by reference. The production of lithiumcobalt oxide, lithium nickel oxide, lithium cobalt nickel oxide, lithiumtitanium oxide and other lithium metal oxides is described in copendingand commonly assigned U.S. patent application Ser. No. 09/595,958, nowU.S. Pat. No. 6,749,648 to Kumar et al., entitled “Lithium MetalOxides,” incorporated herein by reference.

The production of aluminum oxide submicron/nanoscale particles isdescribed in copending and commonly assigned, U.S. patent applicationSer. No. 09/136,483 to Kumar et al., entitled “Aluminum OxideParticles,” incorporated herein by reference. In particular, thisapplication discloses the production of γ-Al₂O₃. The formation ofdelta-Al₂O₃ and theta-Al₂O₃ by laser pyrolysis/light reactive depositionalong with doped-crystalline and amorphous alumina is described incopending and commonly assigned U.S. patent application Ser. No.09/969,025 to Chiruvolu et al., entitled “Aluminum Oxide Powders,”incorporated herein by reference.

Amorphous aluminum oxide materials can be combined with other glassformers, such as SiO₂ and/or P₂O₅. For example, suitable metal oxidedopant(s)/additive(s) for aluminum oxide for optical glass formationcomprise cesium oxide (Cs₂O), rubidium oxide (Rb₂O), thallium oxide(Tl₂O), lithium oxide (Li₂O), sodium oxide (Na₂O), potassium oxide(K₂O), beryllium oxide (BeO), magnesium oxide (MgO), calcium oxide(CaO), strontium oxide (SrO), barium oxide (BaO), and the like andcombinations of any two or more thereof. Glass dopant(s)/additive(s) canaffect, for example, the index-of-refraction, consolidation temperatureand/or the porosity of the glass. Suitable metal oxide dopants/additivesfor infrared emitters comprise, for example, cobalt oxide (CO₃O₄),Er₂O₃, CrO₂, Tm₂O₃, Nd₂O₃, Yb₂O₃, Pr₂O₃, Dy₂O₃, Ho₂O₃, and the like, andcombinations of any two or more thereof.

In addition, tin oxide submicron/nanoscale particles have been producedby laser pyrolysis, as described in U.S. Pat. No. 6,200,674 to Kumar etal., entitled “Tin Oxide Particles,” incorporated herein by reference.The production of zinc oxide submicron/nanoscale particles is describedin copending and commonly assigned U.S. patent application Ser. No.09/266,202, now U.S. Pat. No. 7,423,512 to Reitz et al., entitled “ZincOxide Particles,” incorporated herein by reference. In particular, theproduction of ZnO submicron/nanoscale particles is described.

Submicron/nanoscale particles and corresponding coatings of rare earthmetal oxide particles, rare earth doped metal/metalloid oxide particles,rare earth metal/metalloid sulfides and rare earth doped metal/metalloidsulfides are described in copending and commonly assigned U.S. patentapplication Ser. No. 09/843,195, now U.S. Pat. No. 6,692,660 to Kumar etal, entitled “High Luminescence Phosphor Particles,” incorporated hereinby reference. Suitable host materials for the formation of phosphorscomprise ZnO, ZnS, Zn₂SiO₄, SrS, YBO₃, Y₂O₃, Al₂O₃, Y₃Al₅O₁₂ andBaMgAl₁₄O₂₃, and combinations of any two or more thereof. Exemplarynon-rare earth metals for activating phosphor particles asdopant(s)/additive(s) include, for example, manganese, silver, lead, andthe like and combinations thereof. Exemplary rare earth metals forforming metal oxide phosphors include, for example, europium, cerium,terbium, erbium and the like and combinations thereof. Generally, heavymetal ions or rare earth ions are used as activators in phosphors. Forphosphor applications, the particles are generally crystalline.

The production of iron, iron oxide and iron carbide is described in apublication by Bi et al., entitled “Nanocrystalline α-Fe, Fe₃C, andFe₇C₃ produced by CO₂ laser pyrolysis,” J. Mater. Res. Vol. 8, No. 71666-1674 (July 1993), incorporated herein by reference. The productionof submicron/nanoscale particles of silver metal is described in U.S.Pat. No. 6,394,494 to Reitz et al., entitled “Metal Vanadium OxideParticles,” incorporated herein by reference. Submicron/nanoscale carbonparticles produced by laser pyrolysis is described in a reference by Biet al., entitled “Nanoscale carbon blacks produced by CO₂ laserpyrolysis,” J. Mater. Res. Vol. 10, No. 11, 2875-2884 (November 1995),incorporated herein by reference.

The production of iron sulfide (Fe_(1-x)S) submicron/nanoscale particlesby low rate laser pyrolysis is described in Bi et al., Material ResearchSociety Symposium Proceedings, vol. 286, p. 161-166 (1993), incorporatedherein by reference. Precursors for laser pyrolysis production of ironsulfide were iron pentacarbonyl (Fe(CO)₅) and hydrogen sulfide (H₂S).Other suitable gaseous sulfur precursors for vapor delivery comprise,for example, pyrosulfuryl chloride (S₂O₅Cl₂), sulfur chloride (S₂Cl₂),sulfuryl chloride (SO₂Cl₂), thionyl chloride (SOCl₂), and the like, andcombinations of any two or more thereof. Suitable sulfur precursors foraerosol delivery comprise, for example, ammonium sulfate ((NH₄)₂S),sulfuric acid (H₂SO₄), and the like, and any combinations thereof, whichare soluble in water. Other metal/metalloid sulfide materials can besimilarly produced.

Metal borates can be similarly formed using one or more metal precursorsand a boron precursor. As a specific example, TiB₂ has potential utilityin battery applications. Suitable titanium precursors include, forexample, titanium tetrachloride (TiCl₄), titanium isopropoxide(Ti[OCH(CH₃)₂]₄), and the like, and combinations of any two or morethereof. Suitable boron precursors comprise, for example, borontrichloride (BCl₃), diborane (B₂H₆), BH₃, and the like, and combinationsof any two or more thereof.

Cerium oxide can be produced using the laser pyrolysis apparatusesdescribed above. Suitable precursors for aerosol delivery comprise, forexample, cerous nitrate (Ce(NO₃)₃), cerous chloride (CeCl₃), cerousoxalate (Ce₂(C₂O₄)₃), and the like, and combinations of any two or morethereof. Similarly, zirconium oxide can be produced using the laserpyrolysis apparatuses described above. Suitable zirconium precursors foraerosol delivery comprise, for example, zirconyl chloride (ZrOCl₂),zirconyl nitrate (ZrO(NO₃)₂), and the like, and combinations of any twoor more thereof.

The deposition of coatings of dielectric materials for chip capacitorsis described in copending and commonly assigned U.S. Provisional PatentApplication Ser. No. 60/312,234 to Bryan, entitled “Reactive DepositionFor The Formation Of Chip Capacitors,” incorporated herein by reference.Suitable dielectric materials include a majority of barium titanate(BaTiO₃), optionally mixed with other metal oxides. Other dielectricoxides suitable for incorporation into ceramic chip capacitors withappropriate dopant(s)/additive(s) comprise, for example, SrTiO₃, CaTiO₃,SrZrO₃, CaZrO₃, Nd₂O₃-2TiO₃, La₂O₃-2TiO₂, and the like, and any two ormore thereof.

The production of ternary submicron/nanoscale particles of aluminumsilicate and aluminum titanate can be performed by laser pyrolysisfollowing procedures similar to the production of silver vanadium oxidesubmicro/nanoscale particles described in U.S. Pat. No. 6,394,494 toReitz et al., entitled “Metal Vanadium Oxide Particles,” incorporatedherein by reference. Suitable precursors for the production of aluminumsilicate comprise, for vapor delivery, a mixture of aluminum chloride(AlCl₃), silicon tetrachloride (SiCl₄), and the like, and combinationsthereof, and, for aerosol delivery, a mixture of tetra(N-butoxy) silaneand aluminum isopropoxide (Al(OCH(CH₃)₂)₃), a mixture oftetraethoxysilane and aluminum nitrate, or tetraethoxysilane andaluminum chloride, or tetraethoxysilane and aluminum isopropoxide, andthe like, and combinations of any two or more thereof. Similarly,suitable precursors for the production of aluminum titanate comprise,for aerosol delivery, a mixture of aluminum nitrate (Al(NO₃)₃) andtitanium dioxide (TiO₂) powder dissolved in sulfuric acid, a mixture ofaluminum isopropoxide and titanium isopropoxide (Ti(OCH(CH₃)₂)₄), andthe like, and combinations of any two or more thereof.

The formation of submicron/nanoscale particles along with coatings ofmetal/metalloid compositions with complex anions is described incopending and commonly assigned U.S. patent application Ser. No.09/845,985 to Chaloner-Gill et al., entitled “Phosphate PowderCompositions And Methods For Forming Particles With Complex Anions,”incorporated herein by reference. Suitable polyatomic anions comprise,for example, phosphate (PO₄ ⁻³), sulfate (SO₄ ⁻²), silicate (SiO₄ ⁻⁴),and the like, and combinations of any two or more thereof. Suitablephosphorous precursors for forming the phosphate anion, sulfurprecursors for forming the sulfate anion and silicon precursors forforming the silicate anion are discussed above. Suitable cationscomprise, for example, metal and metalloid cations. Phosphate glassescan be used in a variety of contexts. Phosphate compositions for glassescomprise, for example, aluminum phosphate (AlPO₄), calcium phosphate(Ca₃(PO₄)₂), and the like, and combinations of any two or more thereof.Suitable gaseous phosphate precursor compositions for vapor deliverycomprise, for example, phosphine (PH₃), phosphorus trichloride (PCl₃),phosphorous pentachloride (PCl₅), phosphorus oxychloride (POCl₃),P(OCH₃)₃, and the like, and combinations of any two or more thereof.Suitable phosphorous precursors for aerosol delivery comprise, forexample, (C₂H_(S)O)₃P, (C₂H₅O)₃PO, ammonium phosphate ((NH₄)₃PO₄),ammonium phosphate—dibasic ((NH₄)₂HPO₄), ammonium phosphate—monobasic((NH₄)H₂PO₄), phosphoric acid (H₃PO₄), and the like, and combinations ofany two or more thereof, which are all moderately soluble in water.

The synthesis by laser pyrolysis of silicon carbide and silicon nitrideis described in copending and commonly assigned U.S. patent applicationSer. No. 09/433,202 to Reitz et al., entitled “Particle Dispersions,”incorporated herein by reference. Other metal/metalloid carbides andmeta/metalloid nitrides can be similarly produced.

The formation of a powder coating comprising boron and phosphorous dopedamorphous silica (SiO₂) is described in copending and commonly assignedU.S. patent application Ser. No. 09/715,935, now U.S. Pat. No. 7,575,784to Bi et al. entitled “Coating Formation By Reactive Deposition,”incorporated herein by reference. The doped silica powder coating wasconsolidated into a glass layer. Rare earth metal and other dopants foramorphous particles and powder coatings as well as complex glasscompositions for powder coatings, and in particular, erbium dopedaluminum silicate and aluminum-lanthanum-silicate powder coatings andglasses, are described in copending and commonly assigned U.S. patentapplication Ser. No. 10/099,597 to Home et al., filed on Mar. 15, 2002,now U.S. Pat. No. 6,849,334, entitled “Optical Materials And OpticalDevices,” incorporated herein by reference.

For some host glass forming materials and/or dopant(s)/additive(s) ofparticular interest for optical applications, suitable precursors can bedescribed as a representative listing of precursor materials. Such arepresentative list follows.

Suitable silicon precursors for vapor delivery comprise, for example,silicon tetrachloride (SiCl₄), trichlorosilane (Cl₃HSi), trichloromethylsilane CH₃SiCl₃, tetraethoxysilane (Si(OC₂H₅)₄, also known as ethylsilane and tetraethyl silane), and the like, and combinations of any twoor more thereof. Suitable boron precursors comprise, for example, borontrichloride (BCl₃), diborane (B₂H₆), BH₃, and the like, and combinationsof any two or more thereof. Suitable phosphate precursor compositionsfor vapor delivery comprise, for example, phosphine (PH₃), phosphorustrichloride (PCl₃), phosphorous pentachloride (PCl₅), phosphorusoxychloride (POCl₃), P(OCH₃)₃, and the like, and combinations of any twoor more thereof. Suitable germanium precursors comprise, for example,GeCl₄, and the like, and combinations of any two or more thereof.Suitable titanium precursors comprise, for example, titaniumtetrachloride (TiCl₄), titanium isopropoxide (Ti[OCH(CH₃)₂]₄), and thelike, and combinations of any two or more thereof. Suitable liquid,aluminum precursors comprise, for example, aluminum s-butoxide(Al(OC₄H₉)₃), trimethyl aluminum (Al(CH₃)₃, trimethyl ammonia aluminumAl(CH₃)₃NH₃, and the like, and combinations of any two or more thereof.A number of suitable solid, aluminum precursor compositions areavailable, such compositions comprising, for example, aluminum chloride(AlCl₃), aluminum ethoxide (Al(OC₂H₅)₃), aluminum isopropoxide(Al[OCH(CH₃)₂]₃), and the like, and combinations of any two or morethereof. Suitable tellurium precursors comprise, for example, Te(C₂H₅)₂,Te(CH₃)₂, Te(C₃H₇)₂, Te(C₄H₉)₂, Te(C₃H₄)₂, Te(CH₃C₃H₄)₂, and the like,and combinations of any two or more thereof.

With respect to rare earth metal precursors, suitable precursors forvapor delivery include, for example, erbiumheptafluorodimethyloctanedionate, Er(C₁₁H₁₉O₂)₃, Yb(C₁₁H₁₉O₂)₃,Pr(C₁₁H₁₉O₂)₃, Nb(C₁₁H₁₉O₂)₃, Tm(C₁₁H₁₉O₂)₃, and the like, andcombinations of any two or more thereof. Some representative precursorsfor other desirable metal dopant(s)/additive(s) comprise, for example,liquid zinc precursor compositions, such as diethyl zinc (Zn(C₂H₅)₂),dimethyl zinc (Zn(CH₃)₂), and the like, and combinations of any two ormore thereof. Suitable solid, zinc precursors with sufficient vaporpressure of gaseous delivery comprise, for example, zinc chloride(ZnCl₂), and the like, and combinations of any two or more thereof.Suitable lithium precursors for vapor delivery comprise, for example,solids, such as lithium acetate (Li₂O₂CCH₃), liquids, such as lithiumamide (LiNH₂) dissolved in hexane, and the like, and combinations of anytwo or more thereof.

Suitable silicon precursors for aerosol production comprise, forexample, silicon tetrachloride Si(Cl₄), which is soluble in ether,trichlorosilane (Cl₃HSi), which is soluble in carbon tetrachloride,coilloidal silica, Si(OC₂H₅)₄, which is soluble in alcohol, Si(OCH₃)₄,(CH₃)₃SiOSi(CH₃)₃, and the like, and combinations of any two or morethereof. Similarly, suitable boron precursors for aerosol deliveryinclude, for example, ammonium borate ((NH₄)₂B₄O₇), which is soluble inwater and various organic solvents, B(OC₂H₅)₃, B(C₂H₅)₃, and the like,and combinations of any two or more thereof. Suitable phosphorousprecursors for aerosol delivery comprise, for example, ammoniumphosphate ((NH₄)₃PO₄), ammonium phosphate—dibasic ((NH₄)₂HPO₄), ammoniumphosphate—monobasic ((NH₄)H₂PO₄) and phosphoric acid (H₃PO₄), which areall moderately soluble in water, as well as OP(OC₂H₅)₃, which is solublein alcohol and ether, P(OC₂H₅)₃, OP(OCH₃)₃, and the like, andcombinations of any two or more thereof. Suitable aluminum precursorsfor aerosol delivery comprise, for example, aluminum chloride(AlCl₃.6H₂O), which is soluble in many organic solvents, and aluminumnitrate (Al(NO₃)₃.9H₂O) and aluminum hydroxychloride (Al₂(OH)₅Cl.2H₂O),which are soluble in water, as well as Al(C₂H₅)₃, Al(OC₄H₉)₃,Al(C₅H₇O₂)₃, Al(C₁₈H₃₅O₂)₃, and the like, and combinations of any two ormore thereof. Suitable titanium precursors for aerosol deliverycomprise, for example, Ti(N(CH₃)₂)₄), TiO₂OH, and the like, andcombinations of any two or more thereof. Suitable germanium precursorsfor aerosol delivery comprise, for example, Ge(OC₂H₅)₃, Ge(OCH₃)₄, andthe like, and combinations of any two or more thereof. Suitabletellurium precursors for aerosol delivery comprise, for example TeCl₄,which is soluble in alcohol, and the like, and combinations of any twoor more thereof.

Similarly, rare earth dopant/additive precursor(s) can be supplied as anaerosol. Some representative rare earth precursors suitable for aerosoldelivery are presented below with suitable solvents. Yttrium chloride(YCl₃) and yttrium nitrate (Y(NO₃)₃) are soluble in water. Lanthanumchloride (LaCl₃ and LaCl₃.7H₂O) and lanthanum nitrate hexahydrate(La(NO₃)₃.6H₂O) are soluble in water. Thulium chloride (TmCl₃ andTmCl₃.7H₂O) is soluble in water. Ytterbium chloride (YbCl₃ andYbCl₃.6H₂O) is soluble in water. Praseodymium chloride (PrCl₃ andPrCl₃.7H₂O) and praseodymium nitrate hexahydrate (Pr(NO₃)₃.6H₂O) aresoluble in water. Neodymium chloride (NdCl₃ and NdCl₃.6H₂O) andneodymium nitrate hexahydrate (Nd(NO₃)₃.6H₂O) are soluble in water.Erbium chloride (ErCl₃ and ErCl₃.6H₂O) is soluble in water. Othersuitable rare earth dopant(s)/additive(s) include, for example,Er(NO₃)₃, CeCl₃ and Ce(NO₃)₃.

Other non-rare earth metal dopant(s)/additive(s) also can be deliveredby aerosol. For example, zinc chloride (ZnCl₂) and zinc nitrate(Zn(NO₃)₂) are soluble in water and some organic solvents, such asisopropyl alcohol. Suitable lithium precursors for aerosol delivery fromsolution comprise, for example, lithium acetate (LiCH₃CO₂) and lithiumnitrate (LiNO₃), which are soluble in water and alcohol, lithiumchloride (LiCl), which is somewhat soluble in water, alcohol and someother organic solvents, lithium hydroxide (LiOH), which is somewhatsoluble in water and alcohol, and the like, and combinations of any twoor more thereof. Suitable bismuth precursors for aerosol deliverycomprise, for example, bismuth nitrate (Bi(NO₃)₃), which is soluble indilute aqueous acid solutions, and the like, and combinations of any twoor more thereof. Antimony trichloride (SbCl₃) is soluble in alcohol.Barium azide (Ba(N₃)₂ and Ba(N₃)₂.H₂O) and barium chloride (BaCl₂) aresoluble in water. Other barium compounds suitable for aerosol deliveryinclude, for example, Ba(C₂H₃O₂)₂, Ba(C₂H₃O₂)₂.H₂O, Ba(C₂H₃O₂)₂.H₂O andcombinations thereof. Suitable antimony precursors comprise, forexample, Sb(C₂H₅)₃, Sb(OC₂H₅)₃, Sb₂(C₄H₄O₆)₃.6H₂O and combinationsthereof.

As noted above, fluorine dopant(s)/additive(s) are of interest for someapplications. For phosphate coating silica glasses, a fluoride precurorof particular interest comprises for example, phosphorus trifluoride(PF₃), which is a gas such that it is suitable for vapor delivery into alaser pyrolysis/light reactive deposition chamber. Other fluorideprecursors for vapor and/or aerosol delivery comprises, for example,(C₂H₅O)₃SiF, (C₂H_(S)O)₂SiF₂, (C₂H₅O)SiF₃, (C₂H₅)₂SiF₂, C₂H₅SiF₃,C₆H₅SiF₃, H₂SiF₆.xH₂O, SiF₄, Si₄F₃Cl, SiF₂Cl₂, SiFCl₃, HPO₂F₂,HPF₆.6H₂O, (i-C₃H₇O)₂POF, H₂PO₃F, CF₄, CF₃COCF₃.H₂O, AlF₃, SnF₂, SnF₄,GeF₂, GeF₄, GeF₃Cl, GeF₂Cl₂, GeFCl₃, TiF₄, FCH₉CO₂H, C₂F₆, CCl₂F₂,BF₃.2H₂O, [(CH₃)2N]2BF, C₆H₅BF₂, (4-CH₃C₆H₄)BF₂, (4-CH₃C₆H₄)BF₂, HBF₄,and the like, and combinations of any two or more thereof. Chlorinedopant(s)/additive(s) can be introduced as the chloride of ametal/metalloid element or in similar compounds as fluorine. Carbon andnitrogen dopant(s)/additive(s) can be introduced as elements associatedwith other precursors, and carbon can be supplied as ethylene or otherhydrocarbon.

In general, the selection of the composition of particles and/orcorresponding powder coatings are based on the intended use of thematerials. Similarly, any dopants/additives are similarly selected. Theresulting properties of the particles depend on the compositions,including any dopants/additives and the phase(s), e.g., crystallinity oramorphous character, of the particles as well as, in some embodiments,the particle size and particle size distribution. Desirable propertiesfor some applications are described above in some detail either withrespect to specific compositions or more generally.

Particle Production Apparatus

A variety of particle production methods can be used to form productparticles and powder coatings of interest. In one embodiment, theproduction methods are based on a flowing reaction system in whichflowing reactants from a reactant delivery system are reacted andproduct particles are formed within the flow. In a flowing reactionsystem, the product particles are harvested from the flow. Inparticular, laser pyrolysis is a flowing reaction system in which thereaction of the flowing reactant stream is driven by an intense lightbeam that intersects with the flowing reactant stream.

An appropriate laser pyrolysis apparatus generally comprises a reactionchamber isolated from the ambient environment. A reactant inletconnected to a reactant delivery apparatus generates a reactant streamas a flow through the reaction chamber. A radiation beam path, e.g., alight beam path, intersects the reactant stream at a reaction zone. Thereactant/product stream continues after the reaction zone to an outlet,where the reactant/product stream exits the reaction chamber and passesinto a collection apparatus. For light reactive deposition, the coatingcan be performed in the reaction chamber or in a separate coatingchamber connected to the reaction chamber, as described further below.In some embodiments, the radiation source, such as a laser, is locatedexternal to the reaction chamber, and the light beam enters the reactionchamber through an appropriate window or lens. The dimensions of thereactant inlet(s) can be selected in part to obtain a desired productionrate, although the dimensions of the reactant inlets and the flow rateshould be correlated with the other reaction parameters, as describedabove and below, to obtain desired particle/powder coating properties.

Referring to FIG. 1, a particular embodiment 100 of a laser pyrolysissystem involves a reactant delivery apparatus 102, reaction chamber 104,shielding gas delivery apparatus 106, collection apparatus 108 andradiation (e.g., light) source 110. A first reaction delivery apparatusdescribed below can be used to deliver one or more exclusivelygaseous/vapor reactants. An alternative reactant delivery apparatus isdescribed for delivery of one or more reactants as an aerosol. A furtherreactant delivery apparatus permits delivery of one or more reactants asan aerosol and one or more reactant as a vapor/gas.

Referring to FIG. 2, a first embodiment 112 of reactant deliveryapparatus 102 includes a source 120 of a precursor composition. Forliquid or solid reactants, a carrier gas from one or more carrier gassources 122 can be introduced into precursor source 120 to facilitatedelivery of the reactant. Precursor source 120 can comprise a liquidholding container, a solid precursor delivery apparatus or othersuitable container. The carrier gas from carrier gas source 122 cancomprise either an infrared absorber and/or an inert gas. In someembodiments, the precursor source comprises a flash evaporator thatsupplies a vapor of the precursor at a selected vapor pressure,generally without a carrier gas. The flash evaporator can be connectedto a liquid reservoir to supply liquid precursor. Suitable flashevaporators are available from, for example, MKS Instruments, Inc.,Albuquerque, N. Mex. or can be produced from readily availablecomponents.

The gas/vapor from precursor source 120 can be mixed with gases frominfrared absorber source 124, inert gas source 126 and/or secondaryreactant source 128 by combining the gases in a single portion of tubing130. Tubing 130 can be heated to prevent condensation of precursorswithin the tube. The gases/vapors are combined a sufficient distancefrom reaction chamber 104 such that the gases/vapors become well mixedprior to their entrance into reaction chamber 104. The combinedgas/vapor in tube 130 passes through a duct 132 into channel 134, whichis in fluid communication with reactant inlet 256 (FIG. 1).

A second precursor/reactant can be supplied from second precursor source138, which can be a liquid reactant delivery apparatus, a solid reactantdelivery apparatus, a gas cylinder, a flash evaporator or other suitablecontainer or containers. As shown in FIG. 2, second precursor source 138delivers a second reactant to duct 132 by way of tube 130.Alternatively, mass flow controllers 146 can be used to regulate theflow of gases within the reactant delivery system of FIG. 2. Inalternative embodiments, the second precursor can be delivered through asecond duct for delivery into the reactant chamber through a secondchannel such that the reactants do not mix until they are in thereaction chamber. A laser pyrolysis apparatus with a plurality ofreactant delivery nozzles is described further in copending and commonlyassigned U.S. patent application Ser. No. 09/970,279, now U.S. Pat. No.7,507,382 to Reitz et al., entitled “Multiple Reactant Nozzles For AFlowing Reactor,” incorporated herein by reference. One or moreadditional precursors, e.g., a third precursor, fourth precursor, etc.,can be similarly delivered based on a generalization of the descriptionfor two precursors.

As noted above, the reactant stream can comprise one or more aerosols.The aerosols can be formed within reaction chamber 104 or outside ofreaction chamber 104 prior to injection into reaction chamber 104. Ifthe aerosols are produced prior to injection into reaction chamber 104,the aerosols can be introduced through reactant inlets comparable tothose used for gaseous reactants, such as reactant inlet 134 in FIG. 2.

Referring to FIG. 3A, embodiment 210 of the reactant supply system 102can be used to supply an aerosol to duct 132. Reactant supply system 210comprises an outer nozzle 212 and an inner nozzle 214. Outer nozzle 212has an upper channel 216 that leads to a rectangular outlet 218 at thetop of outer nozzle 212, as shown in the insert in FIG. 3A. Rectangularoutlet 218 has selected dimensions to produce a reactant stream ofdesired expanse within the reaction chamber. Outer nozzle 212 comprisesa drain tube 220 in base plate 222. Drain tube 220 is used to removecondensed aerosol from outer nozzle 212. Inner nozzle 214 is secured toouter nozzle 212 at fitting 224.

The top of inner nozzle 214 can comprise a twin orifice internal mixatomizer 226. Liquid is fed to the atomizer through tube 228, and gasesfor introduction into the reaction chamber are fed to the atomizerthrough tube 230. Interaction of the gas with the liquid assists withdroplet formation.

A plurality of aerosol generators can be used to produce aerosol withinthe reaction chamber or within one or more inlets leading to thereaction chamber. The aerosol generators can be used to generate thesame or different aerosol composition from each other. For embodimentsin which the aerosol generators product aerosols of differentcompositions, the aerosols can be used to introduce reactants/precursorsthat are not easily or conveniently dissolved/dispersed into the samesolvent/dispersant. Thus, if a plurality of aerosol generators is usedto form an aerosol directly within the reaction chamber, the aerosolgenerators can be oriented to mix the reactants or to deliver separatestreams, possibly overlapping, along the reaction zone. If two or moreaerosols are generated within a single inlet nozzle the aerosols can bemixed and flowed within a common gas flow. An inlet nozzle with twoaerosol generators is shown in FIG. 3B. Inlet nozzle 240 includesaerosol generators 242, 244, which generate aerosols directed to outlet246.

Alternatively, aerosol generators can generate aerosols within separateinlets such that the aerosols are combined within the reaction chamber.The use of a plurality of aerosol generators within a single inletnozzle or a plurality of inlet nozzles can be useful for embodiments inwhich it is difficult to introduce desired compositions within a singlesolution/dispersion. Multiple aerosol generators producing aerosolswithin different inlets are described further in copending and commonlyassigned U.S. patent application Ser. No. 09/362,631 to Mosso et al.,entitled “Particle Production Apparatus,” incorporated herein byreference.

In any of these aerosol embodiments, one or more vapor/gasreactants/precursors can also be introduced. For example, the vapor/gasprecursors can be introduced within the aerosol generator itself to helpform the aerosol. In alternative embodiments, the vapor can be deliveredthrough a separate inlet into the delivery channel into which theaerosol is generated such that the vapor and aerosol mix and aredelivered into the reaction chamber through the same reactant inlet. Infurther embodiments, the vapor precursors are delivered into thereaction chamber through separate reactant inlets to combine with theflow comprising the aerosol. In addition, these approaches can becombined for the delivery of a single vapor precursor, different vaporprecursors through different delivery channels or a combination thereof.

An embodiment of an inlet nozzle that is configured for delivery of avapor precursor into a channel with an aerosol for delivery togetherinto a reaction chamber is depicted in FIG. 4. Referring to FIG. 4,aerosol generator 360 delivers an aerosol into channel 362. Channel 362leads to reactant inlet 364 that generally leads into a reactionchamber. Reactant inlet 364 can be positioned, as desired, to deliverthe reactant stream/flow a suitable distance from a radiation pathwithin the reaction chamber. Vapor channel 366 leads into channel 362such that vapor precursors can mix with aerosols from aerosol generator360 for delivery through reactant inlet 364. Vapor channel 366 connectsto a flash evaporator 368, although other vapor sources, such as abubbler or solid vapor source, can be used. Flash evaporator heats aliquid precursor to a temperature to deliver a selected vapor pressureto vapor channel 366. Vapor channel 366 and/or channel 362 can be heatedto reduce or eliminate condensation of vapor reactants. Flash evaporator368 connects to a liquid source 370.

An embodiment of a reactant delivery system is depicted in FIG. 5 forthe delivery of a vapor precursor into the reaction chamberindependently from a reactant flow comprising an aerosol. Referring toFIG. 5, aerosol generator 380 generates an aerosol within channel 382that leads to reactant inlet 384. The aerosol from reactant inlet 382leads to radiation beam 386. Vapor channels 388, 390 deliver vaporreactants into the reaction chamber to mix with the aerosol just beforereaching radiation beam 386.

In alternative embodiments, aerosol precursors can be delivered throughchannels 388, 390 of FIG. 5 while a vapor/gaseous reactant(s) aredelivered through channel 382. For example, a vapor silicon precursorand/or other glass forming host elements can be delivered throughcentral channel 382 while aerosol dopant(s)/additive(s) can be deliveredthrough channels 388, 390. In further embodiments, precursor(s), e.g.,dopant/additive precursor(s), can be delivered to intersect anotherreactant flow at a radiation beam and/or just beyond a radiation beam.If a dopant/additive precursor(s) intersect a reactant/product flow justbeyond a radiation beam, the particles may still be forming such thatthe dopant(s)/additive(s) are introduced into the matrix of theparticles, or the dopant(s)/additive(s) can be associated with hotparticles such that they are incorporated into the final uniformmaterial upon consolidation.

Referring to FIG. 1, the reaction chamber 104 comprises a main chamber250. Reactant supply system 102 connects to the main chamber 250 atinjection nozzle 252. Reaction chamber 104 can be heated to a surfacetemperature above the dew point of the mixture of reactants and inertcomponents at the pressure in the apparatus.

The end of injection nozzle 252 has an annular opening 254 for thepassage of inert shielding gas, and a reactant inlet 256 (left lowerinsert) for the passage of reactants to form a reactant stream in thereaction chamber. Reactant inlet 256 can be a slit, as shown in thelower inserts of FIG. 1. Annular opening 254 has, for example, adiameter of about 1.5 inches and a width along the radial direction fromabout ⅛ in to about 1/16 in. The flow of shielding gas through annularopening 254 helps to prevent the spread of the reactant gases andproduct particles throughout reaction chamber 104.

Tubular sections 260, 262 are located on either side of injection nozzle252. Tubular sections 260, 262 comprise, for example, ZnSewindows/lenses 264, 266, respectively. Windows 264, 266 are about 1 inchin diameter. Windows 264, 266 can comprise cylindrical lenses with afocal length equal to the distance between the center of the chamber tothe surface of the lens to focus the light beam to a point just belowthe center of the nozzle opening. Windows 264, 266 can further comprisean antireflective coating. Appropriate ZnSe lenses are available fromLaser Power Optics, San Diego, Calif. Tubular sections 260, 262 providefor the displacement of windows 264, 266 away from main chamber 250 suchthat windows 264, 266 are less likely to be contaminated by reactantsand/or products. Window 264, 266 are displaced, for example, about 3 cmfrom the edge of the main chamber 250. In place of lenses, reflectiveoptics can be used.

Windows 264, 266 are sealed with a rubber o-ring to tubular sections260, 262 to prevent the flow of ambient air into reaction chamber 104.Tubular inlets 268, 270 provide for the flow of shielding gas intotubular sections 260, 262 to reduce the contamination of windows 264,266. Tubular inlets 268, 270 are connected to shielding gas deliveryapparatus 106. A vacuum, such as supplied by a venturi jet pump, can beconnected to the inlet tube in place of a shielding gas source.

Referring to FIG. 1, shielding gas delivery system 106 comprises inertgas source 280 connected to an inert gas duct 282. Inert gas duct 282flows into annular channel 284 leading to annular opening 254. A massflow controller 286 regulates the flow of inert gas into inert gas duct282. If reactant delivery system 112 of FIG. 2 is used, inert gas source126 can also function as the inert gas source for duct 282, if desired.Referring to FIG. 1, inert gas source 280 or a separate inert gas sourcecan be used to supply inert gas to tubes 268, 270. Flow to tubes 268,270 can be controlled by a mass flow controller 288.

Radiation source 110 is aligned to generate an electromagneticradiation, e.g., light, beam 300 that enters window 264 and exits window266. Windows/lenses 264, 266 define a light path through main chamber250 intersecting the flow of reactants at reaction zone 302. Afterexiting window 266, electromagnetic radiation beam 300 strikes powermeter 304, which also acts as a beam dump. An appropriate power meter isavailable from Coherent Inc., Auburn, Calif. Radiation source 110 can bea laser or an intense conventional light source such as an arc lamp. Inone embodiment, radiation source 110 is an infrared laser, especially aCW CO₂ laser such as an 1800 watt maximum power output laser availablefrom PRC Corp., Landing, N.J.

Reactants passing through reactant inlet 256 in injection nozzle 252result in a reactant stream. The reactant stream passes through reactionzone 302, where reaction involving the metal/metalloid precursorcomposition(s) and dopant/additive precursor composition(s) takes place.Heating of the gases in reaction zone 302 is extremely rapid, roughly onthe order of about 10⁵ degree C./sec depending on the specificconditions. The reaction is rapidly quenched upon leaving reaction zone302, and particles 306 are formed in the reactant/product stream. Thenonequilibrium nature of the process can lead to the production ofsubmircon/nanoparticles with a highly uniform size distribution andstructural homogeneity.

The path of the reactant stream continues to collection nozzle 310.Collection nozzle 310 has a circular opening 312, as shown in the upperinsert of FIG. 1. Circular opening 312 feeds into collection system 108.

The chamber pressure is monitored with a pressure gauge 320 attached tothe main chamber. A suitable chamber pressure for the production of thedesired oxides generally are in the range(s) from about 80 Torr to about650 Torr.

Collection system 108 can comprise a curved channel 330 leading fromcollection nozzle 310. Because of the small size of the particles, theproduct particles follow the flow of the gas around curves. Collectionsystem 108 comprises a filter 332 within the gas flow to collect theproduct particles. Due to curved section 330, the filter is notsupported directly above the chamber. A variety of materials such asTeflon® (polytetrafluoroethylene), stainless steel, glass fibers and thelike can be used for the filter as long as the material is substantiallyinert and has a fine enough mesh to trap the particles. Suitablematerials for the filter include, for example, a glass fiber filter fromACE Glass Inc., Vineland, N.J., cylindrical Nomex® filters from AFEquipment Co., Sunnyvale, Calif. and stainless steel filters from AllCon World Systems, Seaford, Del. Filters can be replaced withelectrostatic collectors.

Pump 334 can be used to maintain collection system 108 at a selectedpressure. It may be desirable to flow the exhaust of the pump through ascrubber 336 to remove any remaining reactive chemicals before ventinginto the atmosphere.

The pumping rate can be controlled by either a manual needle valve or anautomatic throttle valve 338 inserted between pump 334 and filter 332.As the chamber pressure increases due to the accumulation of particleson filter 332, the manual valve or the throttle valve can be adjusted tomaintain the pumping rate and the corresponding chamber pressure.

The apparatus can be controlled by a computer 350. Generally, thecomputer controls the radiation (e.g., light) source and monitors thepressure in the reaction chamber. The computer can be used to controlthe flow of reactants and/or the shielding gas.

The reaction can be continued until sufficient particles are collectedon filter 332 such that pump 334 can no longer maintain the desiredpressure in the reaction chamber 104 against the resistance throughfilter 332. When the pressure in reaction chamber 104 can no longer bemaintained at the desired value, the reaction is stopped, and filter 332is removed. With this embodiment, about 1-300 grams of particles can becollected in a single run before the chamber pressure can no longer bemaintained. A single run generally can last up to about 10 hoursdepending on the reactant delivery system, the type of particle beingproduced and the type of filter being used.

An alternative embodiment of a laser pyrolysis apparatus is shown inFIG. 6. Laser pyrolysis apparatus 400 comprises a reaction chamber 402.The reaction chamber 402 comprises a shape of a rectangularparallelapiped. Reaction chamber 402 extends with its longest dimensionalong the laser beam. Reaction chamber 402 has a viewing window 404 atits side, such that the reaction zone can be observed during operation.

Reaction chamber 402 further comprises tubular extensions 408, 410 thatdefine an optical path through the reaction chamber. Tubular extension408 is connected with a seal to a cylindrical lens 412. Tube 414connects laser 416 or other optical radiation source with lens 412.Similarly, tubular extension 410 is connected with a seal to tube 418,which further leads to beam dump/light meter 420. Thus, the entire lightpath from optical radiation source 416 to beam dump 420 is enclosed.

Inlet nozzle 426 connects with reaction chamber 402 at its lower surface428. Inlet nozzle 426 comprises a plate 430 that bolts into lowersurface 428 to secure inlet nozzle 426. Referring to sectional views inFIGS. 7 and 8, inlet nozzle 426 comprises an inner nozzle 432 and anouter nozzle 434. Inner nozzle 432 can have a twin orifice internal mixatomizer 436 at the top of the nozzle. Suitable gas atomizers areavailable from Spraying Systems, Wheaton, Ill. The twin orifice internalmix atomizer 436 has a fan shape to produce a thin sheet of aerosol andgaseous precursors. Liquid is fed to the atomizer through tube 438, andgases for introduction into the reaction chamber are fed to the atomizerthrough tube 440. Interaction of the gas with the liquid assists withdroplet formation.

Outer nozzle 434 comprises a chamber section 450, a funnel section 452and a delivery section 454. Chamber section 450 holds the atomizer ofinner nozzle 432. Funnel section 452 directs the aerosol and gaseousprecursors into delivery section 454. Delivery section 450 leads to anabout 3 inch by 0.5 inch rectangular outlet 456, shown in the insert ofFIG. 7. Outer nozzle 434 comprises a drain 458 to remove any liquid thatcollects in the outer nozzle. Outer nozzle 434 is covered by an outerwall 460 that forms a shielding gas opening 462 surrounding outlet 456.Inert gas is introduced through inlet 464. The nozzle in FIGS. 7 and 8can be adapted for the delivery of aerosol and vapor precursors asdiscussed above with respect to FIGS. 3-5.

Referring to FIG. 6, exit nozzle 470 connects to apparatus 400 at thetop surface of reaction chamber 402. Exit nozzle 470 leads to filterchamber 472. Filter chamber 472 connects with pipe 474, which leads to apump. A cylindrical filter is mounted at the opening to pipe 474.Suitable cylindrical filters are described above.

Another alternative design of a laser pyrolysis apparatus has beendescribed in U.S. Pat. No. 5,958,348 to Bi et al., entitled “EfficientProduction of Particles by Chemical Reaction,” incorporated herein byreference. This alternative design is intended to facilitate productionof commercial quantities of particles by laser pyrolysis. Additionalembodiments and other appropriate features for commercial capacity laserpyrolysis apparatuses are described in copending and commonly assignedU.S. patent application Ser. No. 09/362,631 to Mosso et al., entitled“Particle Production Apparatus,” incorporated herein by reference.

In one embodiment of a commercial capacity laser pyrolysis apparatus,the reaction chamber and reactant inlet are elongated significantlyalong the light beam to provide for an increase in the throughput ofreactants and products. The embodiments described above for the deliveryof aerosol reactants can be adapted for the elongated reaction chamberdesign. Additional embodiments for the introduction of an aerosol withone or more aerosol generators into an elongated reaction chamber aredescribed in U.S. Pat. No. 6,193,936 to Gardner et al., entitled“Reactant Delivery Apparatuses,” incorporated herein by reference. Acombination of vapor and aerosol precursors can be delivered into thisreaction chamber by generalizing the approaches discussed above withrespect to FIGS. 3-5. These improved reactors and corresponding nozzlescan be adapted for light reactive deposition with vapor precursors,aerosol precursors and combinations thereof.

In general, the laser pyrolysis apparatus with the elongated reactionchamber and reactant inlet is designed to reduce contamination of thechamber walls, to increase the production capacity and/or to makeefficient use of resources. To accomplish these objective(s), theelongated reaction chamber provides for an increased throughput ofreactants and products without a corresponding increase in the deadvolume of the chamber. The dead volume of the chamber can becomecontaminated with unreacted compositions and/or reaction products.Furthermore, an appropriate flow of shielding gas confines the reactantsand products within a flow stream through the reaction chamber. The highthroughput of reactants makes efficient use of the laser energy.

The design of the improved reaction chamber 472 is shown schematicallyin FIG. 9. A reactant inlet 474 leads to main chamber 476. Reactantinlet 474 conforms generally to the shape of main chamber 476. Mainchamber 476 includes an outlet 478 along the reactant/product stream forremoval of particulate products, any unreacted gases and inert gases.The configuration can be reversed with the reactants supplied from thetop and product collected from the bottom, if desired. Shielding gasinlets 480 are located on both sides of reactant inlet 474. Shieldinggas inlets are used to form a blanket of inert gases on the sides of thereactant stream to inhibit contact between the chamber walls and thereactants or products. The dimensions of elongated main chamber 476 andreactant inlet 474 can be designed for high efficiency particleproduction.

Reasonable lengths for reactant inlet 474 for the production of ceramicsubmicron/nanoscale particles, when used with an 1800 watt CO₂ laser,are in the range(s) from about 5 mm to about 1 meter. More specificallywith respect to the reactant inlet, the inlet generally has an elongateddimension in the range(s) of at least about 0.5 inches (1.28 cm), inother embodiments in the range(s) of at least about 1.5 inches (3.85cm), in other embodiments in the range(s) of at least about 2 inches(5.13 cm), in further embodiments in the range(s) of at least about 3inches (7.69 cm), in further embodiments in the range(s) of at leastabout 5 inches (12.82 cm) and in additional embodiments in the range(s)from about 8 inches (20.51 cm) to about 200 inches (5.13 meters). Aperson of ordinary skill in the art will recognize that additionalranges of inlet lengths within these specific ranges are contemplatedand are within the present disclosure. In addition, the inlet can becharacterized by an aspect ratio that is the ratio of the length dividedby the width. If the inlet is not rectangular, the aspect ratio can beevaluated using the longest dimension as the length and the width as thelargest dimension perpendicular to the line segment along the length. Insome embodiments, the aspect ratio is at least about 5, in otherembodiments the aspect ratio is at least about 10 and in furtherembodiments, the aspect ratio is from about 50 to about 400. A person ofordinary skill in the art will recognize that additional ranges ofaspect ratio within these explicit ranges of aspect ratio arecontemplated and are within the present disclosure. Nozzle parametersfor particle production by laser pyrolysis are described further incopending U.S. patent application Ser. No. 10/119,645, now U.S. Pat. No.6,919,054 to Gardner et al., entitled “Reactant Nozzles Within FlowingReactors,” incorporated herein by reference.

To obtain high yields at high production rates, the radiation beam canbe directed in a way to intersect with a significant fraction or theentire reactant flow. Thus, the widest width of the reactant flow can beless than the narrowest width of a radiation beam. If the beam isfocused with a cylindrical lens, the lens can be oriented to focus thebeam orthogonal to the flow such that the beam does not narrow relativeto the width of the flow. Thus, a high production rate can be achievedwhile efficiently using resources. In general, the radiation beam andthe reactant flow can be configured such that effectively none ofreactant flow is excluded from the path of the radiation beam. In someembodiments, the radiation beam intersect with at least about 80 volumepercent of the reactant flow, in other embodiment at least about 90volume percent, in further embodiments at least about 95 volume percentand in additional embodiments at least about 99 volume percent of thereactant flow, which can be considered to exclude effectively none ofthe reactant flow from the path of the radiation beam.

Tubular sections 482, 484 extend from the main chamber 476. Tubularsections 482, 484 hold windows 486, 488 to define a light beam path 490through the reaction chamber 472. Tubular sections 482, 484 can compriseinert gas inlets 492, 494 for the introduction of inert gas into tubularsections 482, 484.

The improved reaction system comprises a collection apparatus to removethe submicron/nanoscale particles from the reactant stream. Thecollection system can be designed to collect particles in a batch modewith the collection of a large quantity of particles prior toterminating production. A filter or the like can be used to collect theparticles in batch mode. Alternatively, the collection system can bedesigned to run in a continuous production mode by switching betweendifferent particle collectors within the collection apparatus or byproviding for removal of particles without exposing the collectionsystem to the ambient atmosphere. A suitable embodiment of a collectionapparatus for continuous particle production is described in U.S. Pat.No. 6,270,732 to Gardner et al., entitled “Particle Collection ApparatusAnd Associated Methods,” incorporated herein by reference.

Referring to FIGS. 10-12 a specific embodiment of a laser pyrolysisreaction system 500 includes reaction chamber 502, a particle collectionsystem 504, laser 506 and a reactant delivery system 508 (describedbelow). Reaction chamber 502 comprises reactant inlet 514 at the bottomof reaction chamber 502 where reactant delivery system 508 connects withreaction chamber 502. In this embodiment, the reactants are deliveredfrom the bottom of the reaction chamber while the products are collectedfrom the top of the reaction chamber.

Shielding gas conduits 516 are located on the front and back of reactantinlet 514. Inert gas is delivered to shielding gas conduits 516 throughports 518. The shielding gas conduits direct shielding gas along thewalls of reaction chamber 502 to inhibit association of reactant gasesor products with the walls.

Reaction chamber 502 is elongated along one dimension denoted in FIG. 10by “w”. A radiation, e.g., light or laser, beam path 520 enters thereaction chamber through a window 522 displaced along a tube 524 fromthe main chamber 526 and traverses the elongated direction of reactionchamber 502. The radiation beam passes through tube 528 and exits window530. In one particular embodiment, tubes 524 and 528 displace windows522 and 530 about 11 inches from the main chamber. The radiation beamterminates at beam dump 532. In operation, the radiation beam intersectsa reactant stream generated through reactant inlet 514.

The top of main chamber 526 opens into particle collection system 504.Particle collection system 504 comprises outlet duct 534 connected tothe top of main chamber 526 to receive the flow from main chamber 526.Outlet duct 534 carries the product particles out of the plane of thereactant stream to a cylindrical filter 536. Filter 536 has a cap 538 onone end. The other end of filter 536 is fastened to disc 540. Vent 542is secured to the center of disc 540 to provide access to the center offilter 536. Vent 542 is attached by way of ducts to a pump. Thus,product particles are trapped on filter 536 by the flow from thereaction chamber 502 to the pump. Suitable pumps were described above.Suitable pumps include, for example, an air cleaner filter for a Saab9000 automobile (Pur-o-lator part A44-67), which comprises waximpregnated paper with Plastisol or polyurethane end caps.

In a specific embodiment, reactant delivery system 508 comprises areactant nozzle 550, as shown in FIG. 13. Reactant nozzle 550 cancomprise an attachment plate 552. Reactant nozzle 550 attaches atreactant inlet 514 with attachment plate 552 bolting to the bottom ofmain chamber 526. In one embodiment, nozzle 550 has four channels thatterminate at four slits 554, 556, 558, 560. Slits 558 and 560 can beused for the delivery of precursors and other desired components of thereactant stream. Slits 554, 556 can be used for the delivery of inertshielding gas. If a secondary reactant is spontaneously reactive withthe vanadium precursor, it can be delivered also through slits 554, 556.One apparatus used for the production of oxide particles had dimensionsfor slits 554, 556, 558, 560 of 3 inches by 0.04 inches.

Coating Deposition

Light reactive deposition is a coating approach that uses an intenseradiation source, e.g., a light source, to drive synthesis of desiredcompositions from a reactant stream. It has similarities with laserpyrolysis in that an intense radiation source drives the reaction.However, in light reactive deposition, the resulting compositions aredirected to a substrate surface where a coating is formed. Thecharacteristics of laser pyrolysis that lead to the production of highlyuniform particles correspondingly can result in the production ofcoatings with high uniformity. In addition, reaction features thatresult in high particle production rates by laser pyrolysis can beadapted for high coating rates in light reactive deposition.

In light reactive deposition, the coating of the substrate can beperformed in a coating chamber separate from the reaction chamber or thecoating can be performed within the reaction chamber. In either of theseconfigurations, the reactant delivery system can be configured similarlyto a reactant delivery system for a laser pyrolysis apparatus for theproduction of particles. Thus, the description of the production ofparticles by laser pyrolysis described above and in the examples belowcan be adapted for coating production using the approaches described inthis section.

If the coating is performed in a coating chamber separate from thereaction chamber, the reaction chamber can be essentially the same asthe reaction chamber for performing laser pyrolysis, although thethroughput and the reactant stream size may be designed to beappropriate for the coating process. For these embodiments, the coatingchamber and a conduit connecting the coating chamber with the reactionchamber replace the collection system of the laser pyrolysis system.

A coating apparatus with a separate reaction chamber and a coatingchamber is shown schematically in FIG. 14. Referring to FIG. 14, thecoating apparatus 566 comprises a reaction chamber 568, a coatingchamber 570, a conduit 572 connecting the reaction apparatus withcoating chamber 570, an exhaust conduit 574 leading from coating chamber570 and a pump 576 connected to exhaust conduit 574. A valve 578 can beused to control the flow to pump 576. Valve 578 can be, for example, amanual needle valve or an automatic throttle valve. Valve 578 can beused to control the pumping rate and the corresponding chamberpressures.

Referring to FIG. 15, conduit 572 from the particle production apparatus568 leads to coating chamber 570. Conduit 572 terminates at opening 582within chamber 570. In some embodiments, opening 572 is located near thesurface of substrate 584 such that the momentum of the particle streamdirects the particles directly onto the surface of substrate 584.Substrate 584 can be mounted on a stage or other platform 586 toposition substrate 584 relative to opening 582. A collection system,filter, scrubber or the like 588 can be placed between the coatingchamber 570 and pump 576 to remove particles that did not get coatedonto the substrate surface.

An embodiment of a stage to position a substrate relative to the conduitfrom the particle production apparatus is shown in FIG. 16. A particlenozzle 590 directs particles toward a rotating stage 592. As shown inFIG. 16, four substrates 594 are mounted on stage 592. More or fewersubstrates can be mounted on a moveable stage with correspondingmodifications to the stage and size of the chamber. Movement of stage592 sweeps the particle stream across a substrate surface and positionsparticular substrate 594 within the path of nozzle 590. As shown in FIG.16, a motor is used to rotate stage 592. Stage 592 can comprise thermalcontrol features that provide for the control of the temperature of thesubstrates on stage 592. Alternative designs involve the linear movementof a stage or other motions. In other embodiments, the particle streamis unfocused such that an entire substrate or the desired portionsthereof is simultaneously coated without moving the substrate relativeto the product flow.

If the coating is performed within the reaction chamber, the substrateis mounted to receive product compositions flowing from the reactionzone. The compositions/particles may not be fully solidified into solidparticles, although quenching may be fast enough to form solidparticles. Whether or not the compositions are solidified into solidparticles, the particles can be highly uniform. In some embodiments, thesubstrate is mounted near the reaction zone. In general, thesubstrate/wafer is placed in the range(s) from about 1 millimeter (mm)to about 1 meter coaxial to the reactant flow vector measured from theradiation beam edge, i.e., the downstream locus of points where theradiation intensity is a factor of 1/e² of the maximum beam intensity,in other embodiments in the range(s) from about 2 mm to 50 centimeters(cm), and in further embodiments in the range(s) from about 3 mm toabout 30 cm, although in some circumstances it is conceived thatdistances less than 1 mm and/or greater than 1 meter can have utility. Aperson of ordinary skill in the art will understand that additionalranges within the explicit ranges of substrate distances are conceivedand are within the present disclosure. If the substrate is closer to thereaction zone, the coating process is more dynamic since the welldefined product flow can be directed to desired substrate locations.However, if the substrate is placed farther away from the reaction zone,the coating process is more static in the sense that a more diffusecloud of product particles is directed at the substrate.

An apparatus 600 to perform substrate coating within the reactionchamber is shown schematically in FIG. 17. The reaction/coating chamber602 is connected to a reactant supply system 604, a radiation source 606and an exhaust 608. Exhaust 608 can be connected to a pump 610, althoughthe pressure from the reactants themselves can maintain flow through thesystem.

Various configurations can be used to sweep the coating across thesubstrate surface as the product leaves the reaction zone. Oneembodiment is shown in FIGS. 18 and 19. A substrate 620 moves relativeto a reactant nozzle 622, as indicated by the right directed arrow. Thereactant nozzle and/or the substrate can move relative to the reactionchamber. Reactant nozzle 622 is located just above substrate 620. Anoptical path 624 is defined by suitable optical elements that direct aradiation, e.g., light, beam along path 624. Optical path 624 is locatedbetween nozzle 622 and substrate 620 to define a reaction zone justabove the surface of substrate 620. The hot particles tend to stick tothe substrate surface. A sectional view is shown in FIG. 19. A particlecoating 626 is formed as the substrate is scanned past the reactionzone.

In general, substrate 620 can be carried on a conveyor 628 or a turret(turntable). In some embodiments, the position of conveyor 628 can beadjusted to alter the distance from substrate 626 to the reaction zone.A change in the distance from substrate to the reaction zonecorrespondingly alters the temperature of the particles striking thesubstrate. The temperature of the particles striking the substrategenerally alters the properties of the resulting coating and theconditions for subsequent processing, such as a subsequent heatprocessing consolidation of the coating. The distance between thesubstrate and the reaction zone can be adjusted empirically to producedesired coating properties. In addition, the stage/conveyor supportingthe substrate can include thermal control features such that thetemperature of the substrate can be adjusted to higher or lowertemperatures, as desired.

A particular embodiment of a light reactive deposition apparatus isshown in FIGS. 20-22. Referring to FIG. 20, process chamber 650comprises a light tube 652 connected to a CO₂ laser (not shown) and alight tube 654 connected to a beam dump. An inlet conduit 656 connectswith a precursor delivery system that delivers vapor reactants andcarrier gases. Inlet conduit 656 leads to process nozzle 658. An exhausttube 660 connects to process chamber 650 along the flow direction fromprocess nozzle 658. Exhaust tube 660 leads to a particle filtrationchamber 662. Particle filtration chamber 662 connects to a pump at pumpconnector 664.

An expanded view of process chamber 650 is shown in FIG. 21. A wafercarrier 666 supports a wafer above process nozzle 658. Wafer carrier 666is connected with an arm 668, which translates the wafer carrier to movethe wafer through the particle stream emanating from the reaction zonewhere the laser beam intersects the precursor stream from process nozzle658. Arm 668 comprises a linear translator that is shielded with a tube.A laser entry port 670 is used to direct a laser beam between processnozzle 658 and the wafer. Unobstructed flow from process nozzle wouldproceed directly to exhaust nozzle 672, which leads to particletransport tube 660.

An expanded view of wafer carrier 666 and process nozzle 658 is shown inFIG. 22. The end of process nozzle 658 has an opening for precursordelivery 674 and a shielding gas opening 676 around precursor opening toconfine the spread of precursor and product particles. Wafer carrier 666comprises a support 678 that connects to process nozzle 658 with abracket 680. A circular wafer 682 is held in a mount 684 such that wafer682 slides within mount 684 along tracks 686 to move wafer 682 into theflow from the reaction zone. Backside shield 688 prevents uncontrolleddeposition of particles on the back of wafer 682. Tracks 686 connect toarm 668.

For any of the coating configurations, the intersection of the flow withthe substrate deflects the trajectory of the flow. Thus, it may bedesirable to alter the position of the reaction chamber outlet toaccount for the change in direction of the flow due to the substrate.For example, it may be desirable to alter the chamber design to directthe reflected flow to the outlet and/or to change the position of theoutlet accordingly.

The temperature of the substrate during the deposition process can beadjusted to achieve particular objectives. For example, the substratecan be cooled during the deposition process since a relatively coolsubstrate can attract the particles to its surface throughthermophoretic force. However, in some embodiments, the substrate isheated, for example to about 500° C., during the deposition process. Inembodiments in which that the substrate is close enough to the reactionzone, the particle may be in a semi-molten state when they reach thesubstrate surface. Semi-molten particles may deform upon impact and maystick better due to the deformation. In addition, the particles tend tocompact and fuse on a heated substrate such that a subsequentconsolidation of the coating into a fused glass or other material isfacilitated if the coating were formed initially on a heated substrate.

The formation of coatings by light reactive deposition, silicon glassdeposition and optical devices in general are described further incopending and commonly assigned U.S. patent application Ser. No.09/715,935, now U.S. Pat. No. 7,575,784 to Bi et al., entitled “CoatingFormation By Reactive Deposition,” incorporated herein by reference, andin copending and commonly assigned PCT application designating the U.S.serial number PCT/US01/32413 to Bi et al. filed on Oct. 16, 2001,entitled “Coating Formation By Reactive Deposition,” incorporated hereinby reference.

The well-defined reactant stream as a sheet of flow leading into thereaction zone tends to spread after the reaction zone due to heat fromthe reaction. If the substrate is swept through the reaction zone nearthe reaction zone, the spreading of the flow may not be significant. Insome embodiments, it may be desirable to coat the substrate from theflow farther away from the reaction zone such that the flow has spreadsignificantly and the entire substrate or desired portion thereof can becoated simultaneously without moving the substrate. The appropriatedistance to obtain a uniform coating of particles depends on thesubstrate size and the reaction conditions. A typical distance of about15 centimeters would be suitable for simultaneously coating an entirewafer with a 4-inch diameter. A general description of ranges of thewafer from the radiation beam is given above.

In embodiments in which the entire substrate surface is simultaneouslycoated, when the composition of the product particle flow is changed intime during the deposition process, the composition of the particleschanges through the thickness of the coating. If the composition ischanged continuously, a continuous composition gradient through thelayer results. For optical materials, generally a continuous compositiongradient layer comprising a continuous composition change from a firstcomposition to a second composition has a thickness of no more thanabout 300 microns, in other embodiments no more than about 150 microns,in further embodiments, in the range(s) from about 250 nm to about 100microns and in still other embodiments in the range(s) from about 1micron to about 50 microns. A person of ordinary skill in the art willrecognize that other ranges and subranges within the explicit ranges arecontemplated and are encompassed within the present disclosure.Alternatively or additionally, gradients can be formed within a layer orlayers, such as parallel to a surface, for example, along one or moredimensions of x-y Cartesian coordinates relative to a z-axis that isnormal to a substrate surface or a layered structure, if the structureis formed in layers.

Alternatively, the composition can be changed incrementally ordiscretely to produce layers with varying composition, which can involvea gradual change in composition between two compositions or discretelayers with discrete composition differences. The resulting transitionmaterial has a step-wise change in composition from a first compositionto a second composition. Generally, the first composition and secondcomposition are the compositions of the adjacent layers (or adjacentcompositions on the same layer) such that the transition materialprovides a gradual transition in composition between the two adjacentlayers (or adjacent compositions). While a transition material can havetwo layers, the transition material generally comprises at least threelayers, in other embodiments at least 4 layers and in furtherembodiments in the range(s) from 5 layers to 100 layers. A person ofordinary skill in the art will recognize that additional range(s) withinthese specific ranges are contemplated and are within the presentdisclosure. The total thickness generally is similar to the continuousgradient layers described in the previous paragraph. Each layer withinthe step-wise transition material generally has a thickness less thanabout 100 microns, in other embodiments less than about 25 microns, infurther embodiments in the range(s) from about 500 nm to about 20microns and in additional embodiments in the range(s) from about 1micron to about 10 microns. The layers within the step-wise transitionmaterial may or may not have approximately equal thickness. Similarly,the step-wise change in composition may or may not take equivalent stepsbetween layers of the transition material.

For the production of discrete structures on a substrate surface, thecomposition of the optical material generally can be different atdifferent locations within the structure. To introduce the compositionvariation, the deposition process itself can be manipulated to producespecific structures. Alternatively, various patterning approaches can beused following the deposition. Patterning following deposition of one ormore coating layers is described further below.

Using the deposition approaches described herein, the composition ofproduct particles deposited on the substrate can be changed during thedeposition process to deposit particles with a particular composition atselected locations on the substrate to vary the resulting composition ofthe optical material along the x-y plane. For example, if the productparticle compositions are changed while sweeping the substrate throughthe product particle stream, stripes or grids can be formed on thesubstrate surface with different particle compositions in differentstripes or grid locations. Using light reactive deposition, the productcomposition can be varied by adjusting the reactants that react to formthe product particle or by varying the reaction conditions. The reactionconditions can affect the resulting composition and/or properties ofproduct particles. For example, the reaction chamber pressure, flowrates, radiation intensity, radiation energy/wavelength, concentrationof inert diluent gas in the reaction stream, temperature of the reactantflow can affect the composition and other properties of the productparticles.

In some embodiments, the reactant flow can comprise vapor and/or aerosolreactants, which can be varied to alter the composition of the products.In particular, concentrations of elements can be changed by varying thecomposition and/or quantity of elements in the flow.

While product particle composition changes can be introduced by changingthe reactant flow composition or the reaction conditions while sweepinga substrate through the product stream, it may be desirable, especiallywhen more significant compositional changes are imposed to stop thedeposition between the different deposition steps involving thedifferent compositions. For example, to coat one portion of a substratewith a first composition and the remaining portions with anothercomposition, the substrate can be swept through the product stream todeposit the first composition to a specified point at which thedeposition is terminated. The substrate is then translated the remainingdistance without any coating being performed. The composition of theproduct is then changed, by changing the reactant flow or reactionconditions, and the substrate is swept, after a short period of time forthe product flow to stabilize, in the opposite direction to coat thesecond composition in a complementary pattern to the first composition.A small gap can be left between the coatings of the first compositionand the second composition to reduce the presence of a boundary zonewith a mixed composition. The small gap can fill in during theconsolidation step to form a smooth surface with a relatively sharpboundary between the two materials.

The deposition process can be generalized for the deposition of morethan two compositions and/or more elaborate patterns on the substrate.In more elaborate processes, a shutter can be used to block depositionwhile the product flow is stabilized and/or while the substrate is beingpositioned. A precision controlled stage/conveyor can precisely positionand sweep the substrate for the deposition of a particular composition.The shutter can be rapidly opened and closed to control the deposition.Gaps may or may not be used to slightly space the different location ofthe compositions within the pattern.

In other embodiments, a discrete mask is used to control the depositionof particles. A discrete mask can provide an efficient and preciseapproach for the patterning of particles. With chemical vapor depositionand physical vapor deposition, a layer of material is built up from anatomic or molecular level, which can involve intimate binding of themask to the underlying substrate at an atomic or molecular level toprevent migration of the material being deposited under the mask toblocked regions. Thus, the coated masks are a coating on the surfacewithout an independent, self-supporting structure corresponding to themask, and the coated mask is chemically or physically bonded to thesurface with atomic level contact along the coated mask. In contrast,with particle deposition as described herein, the particles generallycan be at least macromolecular in size with diameters in the range(s) ofabout 1 nanometers (nm) or more such that a mask with a flat surfaceplaced against another flat surface provides sufficient contact toprevent significant particle migration past the mask. While coated maskscan be effectively used in light reactive deposition, physical masksprovide an efficient alternative to coated masks for patterning asurface. The discrete masks have an intact self-supporting structurethat is not bonded to the surface such that the mask can be removedintact from the surface that is coated. Therefore, the discrete maskapproach herein is different from previous masking approaches adaptedfrom photolithography for vapor deposition approaches.

In these embodiments, the formation of the particle coatingcorrespondingly involves directing a product particle stream at thesubstrate shielded with the discrete mask. The discrete mask has asurface, generally a planar surface, with openings at selectedlocations. The discrete mask blocks the surface except at the openingssuch that particles can deposit on the surface through the openings.Thus, the mask provides for patterning compositions on the surface bythe selected placement of the openings. In some embodiments, suitablediscrete masks comprise a mask with a slit that is narrower than theproduct particle flow such that the deposition process can be veryprecisely controlled. Movement of the slit can form a desired, preciselycontrolled pattern with one or more compositions. After use of adiscrete mask, it can be removed and reused.

In some embodiments, a plurality of masks can be used to depositparticles along a single layer. For example, following deposition of apattern through a first mask, a second complementary mask can be used todeposit material over at least a portion of the surface left uncoveredduring deposition with the first mask. Further complementary masks canbe used to form complex patterns while completing a single layer orportion thereof with a coating having varying chemical composition overthe layer.

Thus, using light reactive deposition, a range of effective approachesare available to vary the chemical composition of optical materialswithin layers and in different layers to form three-dimensional opticalstructures with selected compositions at selected positions within thematerial. The patterning of compositions of optical materials during thedeposition process is described further in copending and commonlyassigned U.S. patent application Ser. No. 10/027,906, now U.S. Pat. No.6,952,504 to Bi et al., entitled “Three Dimensional Engineering ofOptical Structures,” incorporated herein by reference.

As described in detail above, laser pyrolysis apparatuses andcorresponding light reactive deposition apparatuses have been designedfor the production of commercial quantities of submicron/nanoscalepowders and powder coatings. Alternatively or in addition, the inventionprovides that the rate of production and/or deposition of the particlescan be varied substantially, depending on a number of factors (e.g., thestarting materials being utilized, the desired reaction product, thereaction conditions, the deposition efficiency, and the like, andcombinations thereof). Thus, in one embodiment, the rate of particleproduction can vary in the range(s) from about 5 grams per hour ofreaction product to about 10 kilograms per hour of desired reactionproduct. Specifically, using apparatuses described herein, coating canbe accomplished at particle production rates in the range(s) of up to atleast about 10 kilograms per hour (kg/hr), in other embodiments in therange(s) of at least about 1 kg/hr, in further embodiments with lowerproduction rates in the range(s) of at least about 250 grams per hour(g/hr) and in additional embodiments in the range(s) of at least about50 g/hr. A person of ordinary skill in the art will recognize thatproduction rates intermediate between these explicit production ratesare contemplated and are within the present disclosure. Exemplary ratesof particle production (in units of grams produced per hour) include inthe range(s) of not less than about 5, 10, 50, 100, 250, 500, 1000,2500, 5000, or 10000.

Not all of the particles generated are deposited on the substrate. Ingeneral the deposition efficiency depends on the relative speed of thesubstrate through the product stream with the particles, for embodimentsbased on moving the substrate through a sheet of product particles. Atmoderate relative rates of substrate motion, coating efficiencies in therange(s) of not less than about 15 to about 20 percent have beenachieved, i.e. about 15 to about 20 percent of the produced particlesare deposited on the substrate surface. Routine optimization canincrease this deposition efficiency further. At slower relative motionof the substrate through the product particle stream, depositionefficiencies in the range(s) of at least about 40% have been achieved.In some embodiments, the rates of particle production are in therange(s) such that at least about 5 grams per hour, or alternatively orin addition, in the range(s) of at least about 25 grams per hour, ofreaction product are deposited on the substrate. In general, with theachievable particle production rates and deposition efficiencies,deposition rates can be obtained in the range(s) of at least about 5g/hr, in other embodiments in the range(s) of at least about 25 g/hr, infurther embodiments in the range(s) of at least from about 100 g/hr toabout 5 kg/hr and in still other embodiment in the range(s) from about250 g/hr to about 2.5 kg/hr. A person of ordinary skill in the art willrecognize that deposition rates between these explicit rates arecontemplated and are within the present disclosure. Exemplary rates ofparticle deposition (in units of grams deposited per hour) include inthe range(s) of not less than about 0.1, 0.5, 1, 5, 10, 25, 50, 100,250, 500, 1000, 2500, or 5000.

Alternatively or in addition, the invention provides that the rate ofthe movement of the substrate and the particle flow relative to eachother can vary substantially, depending on the desired specificationsfor the coated substrate. Thus, in one embodiment, the rate can bemeasured on an absolute scale, and can vary in the range(s) from about0.001 inches per second to about 12 inches per second, or even more.Further, in another embodiment, the rate can be measured on a scalerelative to the substrate being coated, and can vary in the range(s)from about 0.05 substrates per minute to about 1 substrate per second.

For suitable wafer/substrate sizes, at least a substantial portion ofthe substrate surface can be coated with a sufficient thickness to forma consolidated material at a rate in the range(s) of 2 microns perminute, in other embodiments in the range(s) of at least about 5 micronsper minute, in some embodiments in the range(s) at least about 20microns per minute, and in further embodiments in the range(s) at leastabout 100 microns per minute, in which the thickness refers to a powdercoating sufficiently thick to form a consolidated material at thespecified thickness. A person or ordinary skill in the art willrecognize that additional ranges within these explicit ranges arecontemplated and are within the present disclosure.

For appropriate embodiments using a sheet of product particles, the rateof substrate motion generally is a function of the selected depositionrate and the desired coating thickness as limited by the ability to movethe substrate at the desired rate while obtaining desired coatinguniformity. Due to the high deposition rates achievable with lightreactive deposition, extremely fast coating rates are easily achievable.These coating rates by LRD are dramatically faster than rates that areachievable by competing methods. In particular, at particle productionrates of about 10 kg/hr, an eight-inch wafer can be coated with athickness of about 10 microns of powder in approximately one second evenat a deposition efficiency of only about 2.5 percent, assuming a powderdensity of about 10% of the bulk density. A person of ordinary skill inthe art can calculate with simple geometric principles any one of thefollowing variables based on one or more of the other variables from thegroup of a coating rate, the deposition rate, the desired thickness andthe density of powder on the substrate.

In particular, apparatus designs based on an actuator arm moving asubstrate through the product particle stream within a reaction chamber,as described herein, can straightforwardly move a substrate at rates tocoat an entire eight-inch wafer in about 1 second or less. Generally, inembodiments of particular interest that take advantage of the rapidrates achievable, substrates are coated at rates in the range(s) of atleast about 0.1 centimeters per second (cm/s), in additional embodimentsin the range(s) at least about 0.5 cm/s, in other embodiments in therange(s) at least about 1 cm/s, in further embodiments in the range(s)from about 2 cm/s to about 30 cm/s, and in other embodiments in therange(s) from about 5 cm/s to about 30 cm/s. A person of ordinary skillin the art will recognize that coating rates intermediate between theseexplicit rates are contemplated and are within the present disclosure.

Particle and Coating Properties

Laser pyrolysis/light reactive deposition is particularly suitable forthe formation of highly uniform particles, especiallysubmicron/nanoscale particles. The particles can be collected forfurther processing, or the particles can be directly deposited onto asubstrate to form a particle coating. Small particle size and particleuniformity can contribute overall to the uniformity of the resultingcoating, for example, with respect to composition as well as thesmoothness of the surface and interfaces between materials. Inparticular, the lack of particles significantly larger than the averagecan lead to a more uniform coating.

A collection of particles of interest generally has an average diameterfor the primary particles in the range(s) of less than about 2500 nm, inmost embodiments in the range(s) less than about 500 nm, in additionalembodiments in the range(s) less than about 250 nm, in other embodimentsin the range(s) from about 1 nm to about 100 nm, in some embodiments inthe range(s) from about 2 nm to about 95 nm, in further embodiments inthe range(s) from about 3 nm to about 75 nm, and still other embodimentsin the range(s) from about 5 nm to about 50 nm. A person of ordinaryskill in the art will recognize that other average diameter rangeswithin these specific ranges are also contemplated and are within thepresent disclosure. Particle diameters generally are evaluated bytransmission electron microscopy. Diameter measurements on particleswith asymmetries are based on an average of length measurements alongthe principle axes of the particle. In general, a collection ofparticles, as described herein, has substantially all primary particlesthat are not fused, i.e., hard bonded to remove a distinct separableinterface, although they can be attracted by electrostatic forces, asdescribed below. Powder coatings, which maintain characteristics of theprimary particles, are described further above and below.

Particles refer to dispersable units within the collection of particles.Thus, hard fused primary particles collectively form a particle. Primaryparticles represent distinguishable units in a transmission electronmicrograph, which can be hard fused as indicated by necking or the likein the micrograph. The degree of hard fusing can require some effort toevaluate. In particular, the particles can be dispersed in a liquid inwhich they are insoluble to evaluate how the secondary particle size,i.e., the dispersed particle size, compares with the primary particlesize. To the extent that the secondary particle size is approximatelyequal to the primary particle size, the primary particle have little ifany hard fusing is present. In other words, if the primary particles aresubstantially unfused, the average particle size is approximately equalto the average primary particle size, and the particle size distributionis approximately equal to the primary particle size distribution. Thedispersion of the particles in a liquid can involve some empiricaladjustment to fully disperse the particles with respect to any softfusing, which are generally characterized by weak electrostaticinteractions. The formation of particle dispersions is describedfurther, for example, in copending U.S. patent application Ser. No.09/433,202 to Rietz et al., entitled “Particle Dispersions,” and incopending U.S. patent application Ser. No. 09/818,141, now U.S. Pat. No.6,599,631 to Kambe et al., entitled “Polymer-Inorganic ParticleComposites,” both of which are incorporated by reference.

Depending on the composition of the particles, some particles are moreprone to hard fusing than other particles. Laser pyrolysis/lightreactive deposition provide a versatile approach for forming unfusedparticles with a wide range of compositions. In particular, thereactions conditions can be altered to ensure that substantially no hardfusing of the particles occurs. Specifically, the reactant density canbe selected to be low enough that substantially no hard particle fusingoccurs. The overall reaction conditions can be maintained by theinclusion of inert diluent gas(es) to compensate for the flow changes inthe reactant precursors. The reactant nozzle can be further elongated tomaintain the desired particle production rate while operating underconditions in which substantially no hard particle fusing occurs. Asnoted above, the reactant inlet nozzle can be elongated to large lengthswhile effectively performing laser pyrolysis/light reactive deposition.Thus, high quality substantially unfused particles of desiredcompositions can be formed at high rates based on the disclosure herein.

The primary particles usually have a roughly spherical gross appearance.Upon closer examination, crystalline particles generally have facetscorresponding to the underlying crystal lattice, for crystallineparticles. Nevertheless, crystalline primary particles tend to exhibitgrowth in laser pyrolysis that is roughly equal in the three physicaldimensions to give a gross spherical appearance. Amorphous particlesgenerally have an even more spherical aspect. In some embodiments, inthe range(s) of about 95 percent of the primary particles, and in someembodiments in the range(s) of about 99 percent, have ratios of thedimension along the major axis to the dimension along the minor axisless than about 2.

A variety of chemical particles, generally solid particles, can beproduced by the methods described herein. Solid particles generally aredeposited as powders. For some applications, it is desirable to havevery uniform particles. Processes using focused radiation areparticularly suitable for the formation of highly uniform particles,especially submicron/nanoscale particles. In laser pyrolysis, thecollector generally is placed a sufficient distance from the reactionzone such that the particles are well quenched when they reach thecollector. If the reaction conditions are controlled appropriately, theprimary particles are quenched such that they are formed as independentprimary particles with substantially no hard fusing, i.e.,non-dispersable fusing, to other primary particles.

Because of their small size, the primary particles tend to form looseagglomerates, following collection, due to van der Waals and otherelectromagnetic forces between nearby particles. These agglomerates canbe dispersed to a significant degree or essentially completely, ifdesired. Even though the particles may form loose agglomerates, thesubmicron/nanoscale of the primary particles is clearly observable intransmission electron micrographs of the particles. The particlesgenerally have a surface area corresponding to particles on asubmicron/nanoscale as observed in the micrographs. Furthermore, theparticles can manifest unique properties due to their small size andlarge surface area per weight of material. For example, vanadium oxidesubmicron/nanoscale particles can exhibit substantially high energydensities in lithium batteries, as described in U.S. Pat. No. 5,952,125to Bi et al., entitled “Batteries With Electroactive Nanoparticles,”incorporated herein by reference.

The primary particles can have a high degree of uniformity in size.Laser pyrolysis, as described above, generally results in particleshaving a very narrow range of particle diameters. Furthermore, heatprocessing under suitably mild conditions does not alter the very narrowrange of particle diameters. With aerosol delivery of reactants forlaser pyrolysis, the distribution of particle diameters is particularlysensitive to the reaction conditions. Nevertheless, if the reactionconditions are properly controlled, a very narrow distribution ofparticle diameters can be obtained with an aerosol delivery system. Asdetermined from examination of transmission electron micrographs, theprimary particles generally have a distribution in sizes such that inthe range(s) of at least about 80 percent, in other embodiments in therange(s) of at least about 95 percent, and in some embodiments in therange(s) 99 percent, of the primary particles have a diameter greaterthan about 40 percent of the average diameter and less than about 700percent of the average diameter. IN further embodiments, the primaryparticles generally have a distribution in sizes such that in therange(s) of at least about 80 percent, in other embodiments in therange(s) of at least about 95 percent, and in some embodiments in therange(s) 99 percent, of the primary particles have a diameter greaterthan about 40 percent of the average diameter and less than about 300percent of the average diameter. In alternative or additionalembodiments, the primary particles have a distribution of diameters suchthat in the range(s) of at least about 95 percent, and in furtherembodiments in the range(s) 99 percent, of the primary particles have adiameter greater than about 45 percent of the average diameter and lessthan about 200 percent of the average diameter. A person of ordinaryskill in the art will recognize that other ranges within these explicitranges are contemplated and are within the present disclosure.

Furthermore, in some embodiments no primary particles have an averagediameter in the range(s) of greater than about 10 times the averagediameter, in some embodiments in the range(s) of greater than about 5times the average diameter, in further embodiments in the range(s) ofgreater than about 4 times the average diameter, in additionalembodiments in the range(s) of greater than about 3 times the averagediameter, and in other embodiment in the range(s) greater than about 2times the average diameter. A person of ordinary skill in the art willrecognize that other ranges of distribution cut-offs within theseexplicit ranges are contemplated and are within the present disclosure.In other words, the particle size distribution effectively does not havea tail indicative of a small number of particles with significantlylarger sizes relative to the average size. This cut-off in the particlesize distribution is a result of the small reaction zone andcorresponding rapid quench of the particles. An effective cut off in thetail of the size distribution indicates that there are less than about 1particle in 10⁶ that have a diameter greater than a specified cut offvalue above the average diameter. In some embodiments, the evaluation ofthe lack of a tail can be performed with computational analysis oftransmission electron microscopy micrographs. Narrow size distributions,lack of a tail in the distributions and the roughly spherical morphologycan be exploited in a variety of applications.

In addition, the submicron/nanoscale particles generally have a veryhigh purity level. Furthermore, crystalline submicron/nanoscaleparticles produced by laser pyrolysis can have a high degree ofcrystallinity. Certain impurities on the surface of the particles may beremoved by heating the particles to temperatures below their sinteringtemperatures to achieve not only high crystalline purity but high purityoverall.

When collecting the particles directly onto a substrate surface, thedistance from the substrate to the reaction zone and the temperature ofthe substrate can be adjusted to control the character of the deposit onthe substrate surface. The particles on the surface form a powdercoating. The powder coating can be in the form of independent primaryparticles randomly stacked on the surface. The coating of primaryparticles may only be held together by electromagnetic forces betweenadjacent and nearby particles. In some embodiments, it may be desirableto form a powder coating with some degree of hard fusing between primaryparticles. Fusing between primary particles can be achieved by placingthe substrate closer to the reaction zone such that the particles arenot fully quenched when they strike the substrate surface and/or byheating the substrate, for example, using a wafer heating apparatus, theflame resulting from the reaction of non-particle producing reactants,and/or the gases emanating from the reaction zone during particleproduction. Even if the primary particles are hard fused, the resultingpowder coating maintains character due to the submicron/nanoscale sizeof the primary particles. In particular, primary particles incorporatedinto the powder coating may be visible in scanning electron micrographs.In addition, channels between fused particles generally will reflect thesubmicron/nanoscale of the surrounding fused particles, e.g., by havingsubmicron/nanoscale diameter channels extending into the powder coating.Thus, the submicron/nanoscale character of the primary particles isbuilt into the resulting powder coating formed from thesubmicron/nanoscale primary particles.

While submicron/nanoscale particles can in principle pack densely on asurface due to their small size, the particles tend to coat a surface asa loose collection due to electrostatic forces between the particles.The relative or apparent density of the powder coating can depend on theparticle size, particle composition and the deposition conditions, whichmay affect particle fusing as well as the forces between the particlesand with the surface. The relative density is evaluated relative to thefully densified material of the same composition. In general, therelative density for the powder coating formed from submicron/nanoscaleparticles is in the range(s) of less than about 0.6, in otherembodiments in the range(s) from about 0.02 to about 0.55 and in furtherembodiments in the range(s) from about 0.05 to about 0.4. A person ofordinary skill in the art will recognize that additional ranges withinthese specific ranges are contemplated and are within the presentdisclosure.

To obtain particular objectives, the features of a coating can be variedwith respect to composition of layers of the powders as well as locationof materials on the substrate. Generally, to form an optical device theuniform optical material can be localized to a particular location onthe substrate. In addition, multiple layers of particles can bedeposited in a controlled fashion to form layers with differentcompositions. Similarly, the coating can be made a uniform thickness, ordifferent portions of the substrate can be coated with differentthicknesses of particles. Different coating thicknesses can be appliedsuch as by varying the sweep speed of the substrate relative to theparticle nozzle, by making multiple sweeps of portions of the substratethat receive a thicker particle coating or by patterning the layer, forexample, with a mask. Approaches for the selective deposition ofparticles are described above. Alternatively or additionally, a layercan be contoured by etching or the like following deposition eitherbefore or after consolidation into a uniform material.

Thus, layers of materials, as described herein, may comprise particularlayers that do not have the same planar extent as other layers. Forexample, some layers may cover the entire substrate surface or a largefraction thereof while other layers cover a smaller fraction of thesubstrate surface. In this way, the layers can form one or morelocalized devices. At any particular point along the planar substrate, asectional view through the structures may reveal a different number ofidentifiable layers than at other point along the surface. Generally,for optical applications, the particle coatings have a thickness in therange(s) of less than about 500 microns, in other embodiments, in therange(s) of less than about 250 microns, in additional embodiments inthe range(s) from about 50 nanometers to about 100 microns and infurther embodiments in the range(s) from about 100 nanometers to about50 microns. A person of ordinary skill in the art will recognize thatadditional range(s) within these explicit ranges and subranges arecontemplated and are encompassed within the present disclosure.

Heat Processing

Significant properties of submicron/nanoscale particles can be modifiedby heat processing. Suitable starting material for the heat treatmentinclude particles produced by laser pyrolysis. In addition, particlesused as starting material for a heat treatment process can have beensubjected to one or more prior heating steps under different conditions.For the heat processing of particles formed by laser pyrolysis, theadditional heat processing can improve/alter the crystallinity, removecontaminants, such as elemental carbon, and/or alter the stoichiometry,for example, by incorporation of additional oxygen or another element orremoval of oxygen or another element to change the oxidation state of ametal/metalloid element. Furthermore, a heat processing process can beused to alter the composition of the particles, for example, by theintroduction of another metal/metalloid element into the particles,which can be accompanied by changes in other elements, such as oxygen,also.

In some embodiments of interest, mixed metal/metalloid oxides formed bylaser pyrolysis can be subjected to a heat processing step. This heatprocessing can convert the particles into desired high qualitycrystalline forms, if not formed in a desired form. The heat treatmentcan be controlled to substantially maintain the submicron/nanoscale sizeand size uniformity of the particles from laser pyrolysis. In otherwords, particle size is not compromised significantly by thermalprocessing.

The particles can be heated in an oven or the like to provide generallyuniform heating. The processing conditions generally are mild, such thatsignificant amounts of particle sintering does not occur. Thus, thetemperature of heating preferably is low relative to the melting pointof the starting material and the product material.

The atmosphere over the particles can be static, or gases can be flowedthrough the system. The atmosphere for the heating process can be anoxidizing atmosphere, a reducing atmosphere, a reactive atmosphere (suchas H₂S for sulfidation) or an inert atmosphere. In particular, forconversion of amorphous particles to crystalline particles or from onecrystalline structure to a different crystalline structure ofessentially the same stoichiometry, the atmosphere generally can beinert.

Appropriate oxidizing gases include, for example, O₂, O₃, CO, CO₂, andcombinations thereof. The O₂ can be supplied as air. Reducing gasesinclude, for example, H₂ and NH₃. The oxidizing/reducing nature of thegas flow can be adjusted to yield desired oxidation states ofmetal/metalloid elements in the particles. For example, a reducingatmosphere can be used for the heat treatment of BaMgAl₁₄O₂₃ doped witheuropeum since the europeum is generally supplied in a +3 state while itoperates as a phosphor activator in a +2 state. Oxidizing gases orreducing gases optionally can be mixed with inert gases such as Ar, Heand N₂. When inert gas is mixed with the oxidizing/reducing gas, the gasmixture can include in the range(s) from about 1 percentoxidizing/reducing gas to about 99 percent oxidizing/reducing gas, andmore preferably in the range(s) from about 5 percent oxidizing/reducinggas to about 99 percent oxidizing/reducing gas. Alternatively,essentially pure oxidizing gas, pure reducing gas or pure inert gas canbe used, as desired. Care must be taken with respect to the preventionof explosions when using highly concentrated reducing gases.

The precise conditions can be altered to vary the type ofmetal/metalloid oxide particles that are produced. For example, thetemperature, time of heating, heating and cooling rates, the surroundinggases and the exposure conditions with respect to the gases can all beselected to produce desired product particles. Generally, while heatingunder an oxidizing atmosphere, the longer the heating period the moreoxygen that is incorporated into the material, prior to reachingequilibrium. Once equilibrium conditions are reached, the overallconditions determine the crystalline phase of the powders.

A variety of ovens or the like can be used to perform the heating. Anexample of an apparatus 500 to perform this processing is displayed inFIG. 23. Apparatus 700 includes a jar 702, which can be made from glassor other inert material, into which the particles are placed. Suitableglass reactor jars are available from Ace Glass (Vineland, N.J.). Forhigher temperatures alloy jars can be used to replace the glass jars.The top of glass jar 702 is sealed to a glass cap 704, with a Teflon®gasket 706 between jar 702 and cap 704. Cap 704 can be held in placewith one or more clamps. Cap 704 includes a plurality of ports 708, eachwith a Teflon®bushing. A multiblade stainless steel stirrer 710preferably is inserted through a central port 708 in cap 704. Stirrer710 is connected to a suitable motor.

One or more tubes 712 are inserted through ports 708 for the delivery ofgases into jar 702. Tubes 712 can be made from stainless steel or otherinert material. Diffusers 714 can be included at the tips of tubes 712to disperse the gas within jar 702. A heater/furnace 716 generally isplaced around jar 702. Suitable resistance heaters are available fromGlas-col (Terre Haute, Ind.). One port preferably includes aT-connection 718. The temperature within jar 702 can be measured with athermocouple 718 inserted through T-connection 718. T-connection 718 canbe further connected to a vent 720. Vent 720 provides for the venting ofgas circulated through jar 702. Preferably vent 720 is vented to a fumehood or alternative ventilation equipment.

Preferably, desired gases are flowed through jar 702. Tubes 712generally are connected to an oxidizing/reducing gas source and/or aninert gas source. Oxidizing gas/reducing gas, inert gas or a combinationthereof to produce the desired atmosphere is placed within jar 702 fromthe appropriate gas source(s). Various flow rates can be used. The flowrate preferably is between about 1 standard cubic centimeters per minute(seem) to about 1000 seem and more preferably from about 10 sccm toabout 500 sccm. The flow rate generally is constant through theprocessing step, although the flow rate and the composition of the gascan be varied systematically over time during processing, if desired.Alternatively, a static gas atmosphere can be used.

An alternative apparatus 730 for the heat treatment of modest quantitiesof submicron/nanoscale particles is shown in FIG. 24. The particles areplaced within a boat 732 or the like within tube 734. Tube 734 can beproduced from, for example, quartz, alumina or zirconia. Preferably, thedesired gases are flowed through tube 734. Gases can be supplied forexample from inert gas source 736 or oxidizing gas source 738.

Tube 734 is located within oven or furnace 740. Oven 740 can be adaptedfrom a commercial furnace, such as Mini-Mite™ 1100° C. Tube Furnace fromLindberg/Blue M, Asheville, N.C. Oven 740 maintains the relevantportions of the tube at a relatively constant temperature, although thetemperature can be varied systematically through the processing step, ifdesired. The temperature can be monitored with a thermocouple 742.

For the introduction of a metal/metalloid element into the particles, acomposition comprising the metal/metalloid element can be combined withthe particles prior to or during the heat treatment. For example, thecomposition can be combined with the particles as a solution or as apowder. If the composition is applied as a solution, the solvent shouldnot dissolve the particles, and the solvent generally is removed at theinitial portion of the heating process. In some embodiments, theadditional element(s) can be introduced as a powder of the elementalform of the element, i.e., the un-ionized form of the element.Generally, the composition or elemental powder is mixed with theparticles to get even incorporation into the particles.

Suitable temperature ranges depend on the starting material and thetarget product metal/metalloid oxide. For the processing of manysubmicron/nanoscale particles, the temperature varies in the range(s)from about 150° C. to about 1400° C. The heating generally is continuedfor in the range(s) of greater than about 5 minutes, and typically iscontinued for in the range(s) from about 10 minutes to about 120 hours,in most circumstances in the range(s) from about 10 minutes to about 5hours. A person of ordinary skill in the art will recognize that otherranges within these explicit temperature and heating time ranges arecontemplated and are within the present disclosure. Suitable heatingtimes also depend on the particular starting material and target productas well as the temperature. Some empirical adjustment may be helpful toproduce the conditions appropriate for yielding a desired material.Typically, submicron/nanoscale powders can be processed at lowertemperatures while still achieving the desired reaction. The use of mildconditions avoids significant interparticle sintering resulting inlarger particle sizes. To prevent particle growth, the particlespreferably are heated for short periods of time at high temperatures orfor longer periods of time at lower temperatures. Some controlledsintering of the particles can be performed at somewhat highertemperatures to produce slightly larger, average particle diameters.

As noted above, heat treatment can be used to perform a variety ofdesirable transformations for submicron/nanoscale particles. Forexample, the conditions to convert crystalline VO₂ to orthorhombic V₂O₅and 2-D crystalline V₂O₅, and amorphous V₂O₅ to orthorhombic V₂O₅ and2-D crystalline V₂O₅ are describe in U.S. Pat. No. 5,989,514, to Bi etal., entitled “Processing of Vanadium Oxide Particles With Heat,”incorporated herein by reference. Conditions for the removal of carboncoatings from metal oxide submicron/nanoscale particles is described inU.S. Pat. No. 6,387,531, entitled “Metal (Silicon) Oxide/CarbonComposite Particles,” incorporated herein by reference. Theincorporation of lithium from a lithium salt into metal oxidesubmicron/nanoscale particles in a heat treatment process is describedin U.S. Pat. No. 6,136,287 to Home et al., entitled “Lithium ManganeseOxides And Batteries,” and copending and commonly assigned U.S. patentapplication Ser. No. 09/334,203, now U.S. Pat. No. 6,482,374 to Kumar etal., entitled “Reaction Methods for Producing Ternary Particles,” bothof which are incorporated herein by reference. The incorporation ofsilver metal into vanadium oxide particles through a heat treatment isdescribed in U.S. Pat. No. 6,225,007 to Home et al., entitled “MetalVanadium Oxide,” incorporated herein by reference. For metalincorporation into vanadium oxide, the temperature is generally about200° C. to about 500° C. and in other embodiments from about 250° C. toabout 375° C.

In addition, metal/metalloid oxide particles can be converted to thecorresponding metal/metalloid sulfides by heating the oxide in asulfurizing atmosphere formed by a H₂S gas atmosphere or a CS₂ vaporatmosphere. The metal/metalloid oxides can be heated gently to form thesulfide. Since the sulfides are extremely reactive, the heating can bevery gentle, generally less than about 500° C. and alternatively oradditionally in the range(s) of less than about 300° C. Suitableconcentrations of sulfurizing agent and reaction times can be evaluatedempirically by examining the x-ray diffractograms of the resultingmaterials or by performing an elemental analysis.

Modifying the Composition of Powder Coatings

While the compositions can be selected during deposition byappropriately introducing elements into the reactant stream for particleproduction, alternatively or additionally, the powder coatingcomposition can be modified following formation of the powder coating.In particular, the techniques used for the modification of particlecomposition using a heat treatment can be similarly used to modify thecomposition of powder coatings. The composition modifications of powdercoatings may involve introduction of approximately stoichiometricamounts of element(s) and/or dopant(s)/additive(s). Due to thesubmicron/nanoscale of the primary particles incorporated into thepowder coating, the powder coating has a large surface area thatfacilitates incorporation of the additional element(s) into the initialmaterial. One or more additional elements can be incorporated into thepowder coating by a gentle heating, as described above with respect toparticles, or into a densified material during consolidation of thepowder coating into a uniform material. The additional element(s) can beapplied to the powder coating within the reaction chamber or followingremoval from the reaction/coating chamber. If the element(s) is appliedto the powder coating following removal of the coated substrate from thereaction chamber, the additional element(s) can be applied to powdercoating directly or using electro-migration deposition. In theseapproaches, the powder coating can be partly consolidated prior toinitiating the composition introduction process to stabilize thecoating, generally without removing all of the submicron/nano-structuredcharacter of the coating.

Generally, one or more modifying element is applied as a compositioncomprising the desired element. Any remaining elements in thecompositions generally would volatilize during the heating process,although it is possible that oxygen or other non-metal/metalloidelements from the compositions may also incorporate into the powdercoating. For example, metal/metalloid nitrates during the heat treatmentcan involve the incorporation of the metal/metalloid element into thehost material and the removal of nitrogen oxides to remove thecounter-ions of the composition. The composition can be applied to thepowder coating as a solution, an aerosol, and/or as a powder. Ingeneral, the use of a solution can facilitate the even spread of thecomposition through the powder coating by the flow of the solution overand into the powder coating. The concentration of a solution can beselected to contribute to more even distribution of the composition atdesired amounts of modification element through the use of a volume ofliquid that appropriately wets the powder coating. Surfactants and/orchoice of solvent can be used to reduce surface tension and facilitatesubstantially even spread of the solution. The solvent can be evaporatedprior to or during the heat processing of the powder coating toincorporate the modification element into the powder coating. Anysurfactants can be selected to volatize during the consolidation step.

The reactant delivery system can be used to apply a composition to apowder coating within a reaction chamber. In particular, the compositioncomprising the modifying element can be applied within the coatingapparatus by spraying a solution of the composition through the reactantinlet such that the composition is applied to all or selected portionsof the substrate. The composition comprising the modifying element canbe applied, for example, as an aerosol using an aerosol delivery system.The radiation beam can be either turned off during spraying of thecomposition or turned to a very low power to evaporate a portion of thesolvent without reacting the composition. The reactant delivery systemsdescribed above can be adapted for the delivery of the unreactedcomposition. The coating process can be used to apply an approximatelyeven coating onto the powder coating, e.g., by sweeping the substratethrough a delivery stream of the solution with the modifying element ata constant rate.

Alternatively, the modifying element can be applied to the powdercoating following removal of the powder coating from thereaction/coating chamber. The modifying element can be applied,generally as a composition, as a liquid, aerosol and/or a powder, to thepowder coating, for example, by spraying, brushing, dipping or the like.As with solutions applied within the reaction chamber, the concentrationand other properties of the solution can be selected to obtain evendistribution of the modifying element within the powder coating and/orconsolidated material. Dip coating of the powder coating can be aconvenient approach for obtaining uniform distribution of compositionover the powder coating.

Rather than allowing natural migration of the composition with themodifying element over and through the powder coating, an electric fieldcan be used to drive ions of the modifying element(s) into the hostmatrix. Specifically, modifying element(s) can be introduced intomaterial using electrophoretic or electro-migration deposition. In thisapproach, an electric field is used to drive ions into the host matrixof the powder coating. A solution containing the host ions is contactedwith the powder coating. Generally, an electrode is placed behind thesubstrate coating while a counter electrode is placed within thesolution. More than one electrode of each type can be used, if desired.If the ions of the modifying element(s) are cations, the anode is placedin the solution and the cathode is placed behind the substrate. Thecations are driven toward the cathode. Since the powder coating islocated between the cathode and the anode, the ions are driven into thepowder coating.

An embodiment of an apparatus for performing electro-migrationdeposition of ions of modifying element(s) into a powder coating isshown in FIG. 25. Coated substrate 800 includes substrate 802 and powdercoating 804. Barriers 806 are used to confine dopant/additive solution808 in contact with powder coating 804. First electrode 810 is placedadjacent substrate 802 while second electrode 812 is placed withinsolution 808. Electrodes 810 and 812 are connected to an appropriatepower source 814, such as a battery or an adjustable power supplyconnected to line voltage, to apply the electric current/field betweenthe electrodes.

Parameters affecting the electro-migration process include, for example,current density, solution concentration, and doping time. The currentcan be applied in constant field or in pulses. These parameters can beadjusted to select the deposition rate, concentration of the modifyingelements within the powder coating, depth profile of the modifyingelements, and uniformity of the deposition of the modifying elements.Due to the submicron/nano-structuring of the powder coating, lessclustering of the modifying elements can be expected following theelectro-migration deposition. In addition, multiple modifying elementscan be simultaneously or sequentially introduced into the powder coatingby electro-migration deposition. Multiple elements can be simultaneouslyintroduced by including multiple ions within the solution withconcentrations appropriately selected to yield desired amounts of eachof the modifying elements. Similarly, multiple modifying elements can beintroduced sequentially by changing solutions following deposition of afirst modifying element.

The modifying element, e.g., a dopant(s)/additive(s), can be introducedinto a selected portion of the powder coating by selectively contactingthe solution with only a portion of the powder coating using solutionbarriers. Alternatively or additionally, a portion of the powder coatingcan be covered with a mask, such as conventional resist used inelectronic processing, to block migration of the modifying element intothe masked regions. Referring to an embodiment in FIG. 26, coatedsubstrate 820 is in contact with barrier 822 confining a solution to aportion of the coated substrate. Furthermore, a portion of coatedsubstrate 820 is covered with a mask 824. In this embodiment, the powdercoating is doped in un-masked portions in contact with the solutioncomprising a modifying element. Masking generally is selected to formdesired devices following consolidation of the layers into a uniformmaterial. Multiple modifying elements can be sequentially applied to thesame and/or different, although optionally overlapping, portions of acoated substrate by altering the masking between electro-migrationdeposition of the different modifying elements.

In further embodiments, a composition comprising the desired modifyingelement, e.g., a dopant(s)/additive(s), is reacted separately in thereaction chamber for coating onto a powder coating. Thus, a separatelayer of powder comprising a modifying element can be deposited on topof a host powder. As a particular example, if the host powder is ametal/metalloid oxide, a powder of a modifying metal/metalloid oxide canbe formed as a separate powder coating on top of the host powdercoating. Upon consolidation, the materials fuse into a uniformcomposition that can have approximately uniform distribution ofmodifying element through the material. The amount of powder of themodifying element can be selected to yield the desired levels of themodifying element, e.g., a dopant(s)/additive(s). The coating processescan be repeated to form layers of host powder coating (H) and modifyingpowder coating (D) in desired proportions—HDHDHD . . . or alternativelyHDHDH . . . , with modifying powder coating layers always surrounded byhost layers, except if the modified powder coating layer is at thebottom or the top of the multiple layer coating stack where thesubstrate or surface, respectively, surround one side of the modifiedlayer. Of course, in forming a single host or modifying powder coatinglayer in some embodiments, multiple coating passes can be used in thecoating apparatus with each pass involving a sweep of a substratethrough the reactant/product stream. The number of alternating layerscan be selected to yield the desired total thickness and modifyingelement distribution. In particular, thinner host layers andcorresponding modifying powder coating layers may result in a moreuniform distribution of modifying element within the final consolidatedmaterial. In general, the alternating layers comprise at least one hostlayer and one modifying powder coating layer and in some embodiments inthe range(s) of less than about 50 host layers and less than about 50modifying powder coating layers and in further embodiment in therange(s) from 3 host layers and 2 modifying powder coating layers toless than about 25 host layers and less than about 25 modifying powdercoating layers. A person of ordinary skill in the art will recognizethat other ranges within these explicit ranges are contemplated and arewithin the present disclosure. As noted above, a periodic variation inindex-of-refraction, such as through a composition variation, can beused to form photonic band gap materials.

In general, the various approaches for introducing a modifying elementinto a powder coating can be combined for the introduction of one ormore than one modifying element into a powder coating and, in someembodiments, an ultimate consolidated material. In particular, a methodfor introducing one or more modifying elements, such as adopant(s)/additive(s), during formation of a powder coating and methodsfor introducing modifying elements following deposition of a powdercoating are described above. For example, a particular modifying elementcan be introduced using a plurality of techniques to achieve desiredlevels of modifying element and/or distributions of modifying elementwithin the powder coating and/or consolidated material. In addition, forthe deposition of a plurality of modifying elements, each modifyingelement can be deposited using one or more of the techniques describedabove, for convenience of processing and/or to achieve desiredproperties of the resulting consolidated materials.

Consolidation to Form Optical Materials

Heat treatment can sinter the particles and lead to compaction, i.e.,densification, of the powders to form the desired material density, suchas an optical material. This sintering of the particles is generallyreferred to as consolidation. The completely consolidated or densifiedmaterial is generally a uniform material, i.e., it is generally not aporous network, although there can be random imperfections in theuniformity of the material. A partially consolidated or densifiedmaterial is one in which the pore network remains but the pore size hasbeen reduced and the solid matrix strengthened through the fusing ofparticles to form rigid interparticle necks. To consolidate, i.e.,densify, the optical materials, the materials can be heated to atemperature above the melting point for crystalline materials or theflow temperature for amorphous materials, e.g., above the glasstransition temperature and possibly above the softening point belowwhich a glass is self-supporting, to consolidate the coating into adensified material. Consolidation can be used to form amorphous,crystalline or polycrystalline phases in layers. These layers can becompletely or partially densified. In general, consolidation can beperformed before or after patterning of a layer. A preliminary heattreatment can be applied with the reactor flame to reducedopant(s)/additive(s) migration during the consolidation process and topartly densify the material. Using the techniques described herein,doped glasses can be formulated into planar optical devices.

Generally, the heating is performed under conditions to lower theviscosity of the material to promote flow. To form the viscous liquid,crystalline particles are heated above their melting point and amorphousparticles are heated above their glass transition temperature. Becauseof the high viscosity, the material generally does not flowsignificantly on the substrate surface, although small gaps may fill in.Processing at higher temperatures to reduce the viscosity of the meltcan result in undesirable melting of the substrate, migration ofcompositions between layers or in flow from a selected area of thesubstrate. The heating and quenching times can be adjusted to change theproperties of the consolidated coatings, such as density. While thefinal consolidated material may be uniform, the density of the materialmay vary slightly depending on the processing conditions. In addition,heat treatment can remove undesirable impurities and/or change thestoichiometry and crystal structure of the material, as describedfurther above with respect to modification of composition using heattreatment.

Following deposition of the powder layer, the precursors can be shut offsuch that the reactant stream only comprises a fuel and an oxygen sourcethat reacts to form gaseous/vapor products without particles. The flameresulting from the reaction of the fuel and oxygen source can be used toheat the coated substrate without depositing any additional materials onthe substrate. Such a heating step is observed to reducedopant(s)/additive(s) migration upon full consolidation of a dopedsilica glass. A flame heating step can be performed between coatingsteps for several layers or after deposition of several layer, in whicheach coating layer may or may not have the same composition as otherlayers. Generally, after a desired number of layers or quantity ofmaterial is deposited, a final consolidating heat treatment is performedto fully consolidate the material. In forming a coating with a uniformcomposition, one or more layers of particles with the same compositioncan be deposited. All of the layers can be deposited prior to anyconsolidation or partial consolidation, e.g., with a flame, or completeor partial consolidation can be performed after each layer or subset oflayers formed with particles having the same composition. After finalconsolidation, a layer formed with particles of a uniform compositioncan have some variation in dopant/additive concentration(s) through thethickness of the material due to migration of dopant(s)/additive(s)during the consolidation process.

Suitable processing temperatures and times generally depend on thecomposition of the particles. Small particles on the submicron/nanometerscale generally can be processed at lower temperatures and/or forshorter times relative to powders with larger particles due to lowermelting points for the submicron/nanoscale particles in comparison withbulk material. However, it may be desirable to use a comparable meltingtemperature to obtain greater surface smoothness from improved meltingof the submicron/nanoscale particles.

For the processing of silicon oxide submicron/nanoscale particles, theparticle coatings can be heated to a temperature in the range(s) fromabout 800° C. to 1700° C., although with silicon substrates the upperlimit can be about 1350° C. Higher temperatures can be reached withappropriate ceramic substrates. Dopant(s)/additive(s) in the siliconoxide particles can lower the appropriate consolidation temperatures.Thus, the dopant(s)/additive(s) can be selected to flow into a uniformoptical material at a lower temperature. Suitable dopant(s)/additive(s)to lower the flow temperature when placed into silicon oxide (SiO₂)include, for example, boron, phosphorous, germanium, fluorine,germanium, aluminum, sodium, calcium, and combinations thereof. Theamount and composition of one or more dopants/additives can be selectedto yield a desired flow temperature for consolidation andindex-of-refraction of the consolidated optical material.

Heat treatments can be performed in a suitable oven. It may be desirableto control the atmosphere in the oven with respect to pressure and/orthe composition of the gases. Suitable ovens comprise, for example, aninduction furnace, a box furnace or a tube furnace with gas(es) flowingthrough the space containing the coated substrate. The heat treatmentcan be performed following removal of the coated substrates from thecoating chamber. In alternative embodiments, the heat treatment isintegrated into the coating process such that the processing steps canbe performed sequentially in the apparatus in an automated fashion.

For many applications, it is desirable to apply multiple particlecoatings with different compositions. In general, these multipleparticle coatings can be arranged adjacent to each other across the x-yplane of the substrate being coated (e.g., perpendicular to thedirection of motion of the substrate relative to the product stream), orstacked one on top of the other across the z plane of the substratebeing coated, or in any suitable combination of adjacent domains andstacked layers. Each coating can be applied to a desired thickness.

For some embodiments, different compositions can be deposited adjacentto each other and/or in alternating layers. Similarly, distinct layersof different compositions can be deposited in alternating layers.Specifically, two layers with different compositions can be depositedwith one on top of the other, and or additionally or alternatively, withone next to the other, such as layer A and layer B formed as AB. Inother embodiments, more than two layers each with different compositionscan be deposited, such as layer A, layer B and layer C deposited asthree sequential (e.g., stacked one on top of the other, or adjacent tothe other, or adjacent and stacked) layers ABC. Similarly, alternatingsequences of layers with different compositions can be formed, such asABABAB . . . or ABCABCABC . . . . Other combinations of layers can beformed as desired.

Individual uniform layers, each of a particular composition, generallyhave after consolidation an average thickness in the range(s) of lessthan 100 microns, in many embodiments in the range(s) from about 0.1micron to about 50 microns, in other embodiments in the range(s) fromabout 0.2 microns to about 20 microns. A person of skill in the art willrecognize that ranges within these specific ranges are contemplated andare within the scope of the present disclosure. Each uniform layerformed from particles with the same composition can be formed from oneor more passes through a product flow in a light reactive depositionapparatus. Thickness is measured perpendicular to the projection planein which the structure has a maximum surface area.

The material with multiple particle coatings can be heat treated afterthe deposition of each layer or following the deposition of multiplelayers or some combination of the two approaches. The optimal processingorder generally would depend on the melting point of the materials.Generally, however, it is desirable to heat treat and consolidate aplurality of layers simultaneously. Specifically, consolidating multiplelayers simultaneously can reduce the time and complexity of themanufacturing process and, thus, reduce manufacturing costs. If theheating temperatures are picked at reasonable values, the meltedmaterials remain sufficiently viscous that the layers do not mergeundesirable amounts at the interface. Slight merging of the layersgenerally does not affect performance by unacceptable amounts. Bychanging reaction conditions, such as precursor flow or total gas flow,particles can be deposited with changing particle size in thez-direction within a single layer or between layers. Thus, smallerparticles can be deposited on top of larger particles. Since the smallerparticles generally soften at lower temperatures, the consolidation ofthe upper layer can be less likely to damage the lower layers during theconsolidation step. To form patterned structures following deposition,patterning approaches, such as lithography and photolithography, alongwith etching, such as chemical etching, dry etching or radiation-basedetching, can be used to form desired patterns in one or more layers.This patterning generally is performed on a structure prior todeposition of additional material. Patterning can be performed onparticle layers or consolidated layers.

EXAMPLES

While the emphasis herein is on the high rate production of particles,the following examples demonstrate the ability to generate particlesover a range of rates. The examples however demonstrate the ability ofusing laser pyrolysis with or without additional processing to generatea range of inorganic particle compositions. Using the descriptionherein, the processes of the examples can be scaled up to higherproduction rates, over the ranges specified. In general, the scale up isperformed to maintain equivalent reaction conditions such thatcomparable product particles are produced. In particular, the chamberpressure, laser intensity, reactant density in the reaction zone andflow rate can be adjusted to match the conditions of a particularexample at a particular flow rate. The reactant inlet can be increasedin length to generate the desired overall reactant flow rate andparticle production rate. Further descriptions of nozzle designs arefound in copending U.S. patent application Ser. No. 10/119,645, now U.S.Pat. No. 6,919,054 to Gardner et al., entitled “Reactant Nozzles WithinFlowing Reactors,” incorporated herein by reference.

Example 1 Single Phase V₂O₅

The synthesis of V₂O₅ described in this example was performed by laserpyrolysis. The VOCl₃ (Strem Chemical, Inc., Newburyport, Mass.)precursor vapor is carried into the reaction chamber by bubbling Ar gasthrough the VOCl₃ liquid stored in a container at room temperature. Thereactant gas mixture containing VOCl₃, Ar, O₂ and C₂H₄ is introducedinto the reactant gas nozzle for injection into the reactant chamber.The reactant gas nozzle had an opening with dimensions as specified inTable 1. C₂H₄ gas acts as a laser absorbing gas. Argon was used as aninert gas.

The synthesized vanadium oxide nanoscale particles can be directlyhandled in the air. The production rate was typically about 5-10 g/hourof nanoparticles. Based on the teachings herein both above and in thisexample, the particles described in this example can be produced withequivalent properties in appropriate apparatuses and at appropriateconditions at rates in the range(s) of at least about 35 grams per hourand at higher rates described above. The samples were subsequentlyexamined by transmission electron microscopy (TEM) to determine particlesizes and by x-ray diffraction to evaluate the composition andstructure.

Using laser pyrolysis, both amorphous V₂O₅ and 2-D crystalline V₂O₅ havebeen produced. Representative reaction conditions used to produce theseparticles are described in the following table.

TABLE 1 Phase V₂O₅ V₂O₅ V₂O₅ V₂O₅ Crystal Amorphous Amorphous Amorphous2D Crystal Structure Battery 182 146 Capacity (mAh/g) Pressure (Torr)135 142.5 110 300 Argon-Win. 700 700 700 700 (sccm) Argon-Sld. 0.98 0.982.1 1.12 (slm) Ethylene 603 1072 173 268 (sccm) Carrier Gas 116(Ar)676(Ar) 140(Ar) 676(Ar) (sccm) Oxygen (sccm) 284 642 88 400 Laser Output180 215 150 67 (watts) Nozzle Size ⅝″ × 1/16″ ⅝″ × 1/16″ ⅝″ × ⅛″ ⅝″ ×1/16″ sccm = standard cubic centimeters per minute slm = standard litersper minute Argon-Win. = argon flow through inlets 216, 218 Argon-Sld. =argon flow through annular channel 142

Representative x-ray diffractograms for amorphous V₂O₅ and 2-D V₂O₅ areshown in FIGS. 27 and 28, respectively. The x-ray diffractograms wereobtained using Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. Referring to FIG. 27, the broad peaks centered around20Θ˜28 degrees and 58 degrees are typical of amorphous phase of vanadiumoxide. See, U.S. Pat. No. 4,675,260. The amorphous nature of the sampleis confirmed by transmission electron microscopy examination as shown inFIG. 29. The TEM micrograph shows a material that has disordered atomicarrangement.

The diffractogram in FIG. 28 corresponds to a recently reported 2-Dcrystal structure for V₂O₅.

Example 2 Single Phase VO₂

These particles were produced using a similar laser pyrolysis set up asdescribed in Example 1. The reactant gas nozzle had dimensions ⅝ in×1/16 in. For the production of VO₂, C₂H₄ was bubbled through the VOCl₃liquid precursor at room temperature. Representative reaction conditionsfor the production of this material are described in Table 2.

TABLE 2 Phase VO₂ VO₂ VO_(1.27) Crystal Structure Monoclinic MonoclinicTetragonal Battery Capacity (mAh/g) 249 118.4 Pressure (Torr) 320 127200 Argon-Win (sccm) 700 700 700 Argon-Sld. (slm) 5.6 0.98 2.8 Ethylene(sccm) 460 268 402 Carrier Gas (sccm) 460(Ethyl.) 676(Ar) 402(Ethyl.)Oxygen (sccm) 36 200 196 Laser Output (watts) 96 220 100

An x-ray diffractogram of representative product nanoparticles is shownin FIG. 30. Clear diffraction peaks corresponding to a monocliniccrystalline structure are visible. The identified structure from thediffractogram is almost identical to that of the corresponding bulkmaterial, which has larger particle sizes. Therefore, the novelnanoparticle materials have distinct properties while maintaining thesame crystalline lattice of the bulk material. Based on the teachingsherein both above and in this example, the particles described in thisexample can be produced with equivalent properties in appropriateapparatuses and at appropriate conditions at rates in the range(s) of atleast about 35 grams per hour and at higher rates described above.

TEM photos at both high and low magnifications were obtained ofrepresentative nanoparticles with similar x-ray diffraction patterns, asshown in FIGS. 31 and 32. An approximate size distribution wasdetermined by manually measuring diameters of the particles shown inFIG. 32. The distribution of diameters is shown in FIG. 33. An averageparticle size of about 22 nm was obtained. Only those particles showingclear particle boundaries were measured and recorded to avoid regions ofdistorted in the micrograph. This should not bias the measurementsobtained since the single view of the micrograph may not show a clearview of all particles because of the orientation of the crystals. It issignificant that the particles span a rather narrow range of sizes. Inthis case, the largest to the smallest particles differ by no more thanabout 15 nm. Crystallinity of the particles is confirmed in FIG. 31where the underlying lattice structure is visible.

Example 3 Single Phase VO_(1.27)

The experimental arrangement for the production of VO_(10.27) is thesame as that described in Example 2. Representative conditions used toproduce these particles are given in Table 2, above. Based on theteachings herein both above and in this example, the particles describedin this example can be produced with equivalent properties inappropriate apparatuses and at appropriate conditions at rates in therange(s) of at least about 35 grams per hour and at higher ratesdescribed above.

The x-ray diffractogram for this material is shown in FIG. 34, and ischaracteristic of crystalline VO_(1.27) material.

Example 4 V₆O₁₃/VO₂ Mixed Phase Material

The experimental configuration was the same as described with respect toExample 1. The reactant gas nozzle had dimensions ⅝ in×⅛ in. Theparticular experimental parameters are given in Table 3.

TABLE 3 Phase V₆O₁₃ + VO₂ V₆O₁₃ + VO₂ VO₂ + V₂O₃ Crystal StructureMonoclinic Monoclinic Pressure (Torr) 110 110 410 Argon-Win (sccm) 700700 700 Argon-Sld. (slm) 2.1 2.1 11.2 Ethylene (sccm) 173 209 460Carrier Gas (sccm) 140(Ar) 140(Ar) Ethylene Oxygen (sccm) 88 88 36 LaserOutput (watts) 192 100 90

A characteristic x-ray diffractogram of the nanoparticles is shown inFIG. 35. The diffractogram contains a combination of peaks identifiablewith both crystalline V₆O₁₃ and crystalline VO₂. Both types of crystalsare monoclinic. The V₆O₁₃ phase is the majority phase. Appropriatereaction conditions should yield single phase V₆O₁₃. Based on theteachings herein both above and in this example, the particles describedin this example can be produced with equivalent properties inappropriate apparatuses and at appropriate conditions at rates in therange(s) of at least about 35 grams per hour and at higher ratesdescribed above.

Example 5 VO₂/V₉O₃ Mixed Phase Material

The experimental configuration was the same as described with respect toExample 4. The reactant gas nozzle had dimensions ⅝ in× 1/16 in.Representative experimental parameters to produce these particles aregiven in Table 3, above. The x-ray diffractogram is shown in FIG. 36.The diffractogram contains a combination of peaks identifiable with bothcrystalline VO₂ and crystalline V₂O₃. Note that the conditions for theproduction of these particles involves a reduced amount of O₂ relativeto the other gases in the reactant stream. Based on the teachings hereinboth above and in this example, the particles described in this examplecan be produced with equivalent properties in appropriate apparatusesand at appropriate conditions at rates in the range(s) of at least about35 grams per hour and at higher rates described above.

Example 6 Crystalline V₉O₅—Oven Processed

A first sample of crystalline V₉O₅ was produced from amorphous V₂O₅ bybaking the amorphous particles in an oven for 16.0 hours. The amorphousV₂O₅ starting material was produced by laser pyrolysis according to theparameters in the second column of Table 1. The oven was set at atemperature of 202° C. Oxygen gas flowed through a 1.0 in. diameterquartz tube at a flow rate of 105.6 sccm. Between about 100 and about300 mg of nanoparticles were placed within an open 1 cc vial within thetube in the oven. The resulting nanoparticles were single phasecrystalline V₂O₅ nanoparticles. The corresponding x-ray diffractogram ispresented in FIG. 37.

A second sample of crystalline V₂O₅ were made from crystalline VO₂ usingthe same starting materials. The starting materials were crystalline VO₂nanoparticles produced by laser pyrolysis using the conditions specifiedin the second column of Table 2. The second sample was treated in anoven under the same conditions as the first sample.

The resulting nanoparticles for the second sample were single phaseV₂O₅. These had a smaller average diameter than the particles from thefirst sample because of the smaller size of the starting nanoparticlesused to produce the second sample. An x-ray diffractogram for the secondsample is shown in FIG. 38. Based on the teachings herein both above andin this example, the particles described in this example can be producedwith equivalent properties in appropriate apparatuses and at appropriateconditions at rates in the range(s) of at least about 35 grams per hourand at higher rates described above.

Example 7 Laser Pyrolysis for Formation of Amorphous SiO_(x)

The synthesis of silicon oxide particles described in this example wasperformed by laser pyrolysis. The particles were produced usingessentially the laser pyrolysis apparatus of FIG. 1, described above.

The silicon tetrachloride (Strem Chemical, Inc., Newburyport, Mass.)precursor vapor was carried into the reaction chamber by bubbling Ar gasthrough SiCl₄ liquid in a container at room temperature. C₂H₄ gas wasused as a laser absorbing gas, and Argon was used as an inert gas. Thereaction gas mixture containing SiCl₄, Ar, O₂ and C₂H₄ was introducedinto the reactant gas nozzle for injection into the reaction chamber.The reactant gas nozzle had an opening with dimensions as specified inthe last row of Table 4. Additional parameters of the laser pyrolysissynthesis relating to the particles also are specified in Table 4.

TABLE 4 Sample 1 2 3 4 Crystal Amorphous Amorphous Amorphous AmorphousStructure Pressure (Torr) 210 180 360 240 Argon-Win. 700 700 700 700(sccm) Argon-Sld. 5.6 7.0 2.0 5.6 (slm) Argon-Dil. 1120 0.0 0.0 0.0(sccm) Ethylene 1340 980 670 603 (sccm) Carrier Gas 162(Ar) 196(Ar)224(Ar) 224(Ar) (sccm) Oxygen (sccm) 840 636 308 412 Laser Output 830620 520 236 (watts) Nozzle Size ⅝ in × ⅝ in × ⅝ in × ⅝ in × ⅛ in ⅛ in ⅛in ⅛ in sccm = standard cubic centimeters per minute slm = standardliters per minute Argon-Win. = argon flow through inlets 216, 218Argon-Sld. = argon flow through annular channel 142 Argon-Dil. =additional argon added to the reaction stream besides the argon carriergas.The use of additional argon gas to dilute the reaction stream resultedin production of particles that were less agglomerated.

The production rate of silicon oxide particles was typically about 30g/hr. Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

Under the four sets of conditions specified in Table 4, amorphoussilicon oxide particles were produced. To evaluate the atomicarrangement, the samples were examined by x-ray diffraction using theCu(Kα) radiation line on a Siemens D500 x-ray diffractometer. An x-raydiffractogram for a sample produced under the conditions specified inthe first column of Table 4 is shown in FIG. 39. The broad peak in FIG.39 is indicative of an amorphous sample. The other samples yieldedcomparable x-ray diffraction peaks.

Transmission electron microscopy (TEM) was used to determine particlesizes and morphology. A TEM micrograph for the particles produced underthe conditions of the first column of Table 4 is displayed in FIG. 40.An examination of a portion of the TEM micrograph yielded an averageparticle size of about 7 nm. The corresponding particle sizedistribution is shown in FIG. 41. The approximate size distribution wasdetermined by manually measuring diameters of the particles distinctlyvisible in the micrograph of FIG. 40. Only those particles having clearparticle boundaries were measured to avoid regions distorted or out offocus in the micrograph. Measurements so obtained should be moreaccurate and are not biased since a single view cannot show a clear viewof all particles. It is significant that the particles span a rathernarrow range of sizes.

For particles produced under the conditions specified in the fourthcolumn of Table 4, the BET surface area was determined to be 264 m²/gramwith an N₂ gas absorbate. The BET surface area was measured by ParticleTechnology Labs., Ltd., Downers Grove, Ill.

The stoichiometry of the particles was not determined directly. Theparticles had a dark color upon visual inspection. The darkness may havebeen the result of oxygen deficiencies relative to silicon dioxide or todeposits on the particles of elemental carbon from the ethylene in thereactant stream. The dark color was eliminated upon heating in an oxygenenvironment in an oven as described in the following example.

Example 8 Oven Processed

A sample of silicon oxide nanoparticles produced by laser pyrolysisaccording to the conditions specified in the fourth column of Table 4were heated in an oven under oxidizing conditions. The oven wasessentially as described above with respect to FIG. 24. The samples wereheated in the oven at about 500° C. for about 2 hours. Oxygen gas wasflowed through a 1.0 in diameter quartz tube at a flow rate of about 150sccm. Between about 100 and about 300 mg of nanoparticles were placed inan open 1 cc vial within the quartz tube projecting through the oven.The resulting particles were white particles. The x-ray diffractogram isshown in FIG. 42. The sharp peaks at about 45° and about 65° are due tothe aluminum sample holder. The peak at about 7° is an artifact of theinstrument. An additional peak appears at about 12° indicative of asecond amorphous phase of silicon oxide. Based on the color of theheated particles, the heating process evidently either removed elementalcarbon associated with the particles or added oxygen to the particles toshift the stoichiometry toward SiO₂. Based on the teachings herein bothabove and in this example, the particles described in this example canbe produced with equivalent properties in appropriate apparatuses and atappropriate conditions at rates in the range(s) of at least about 35grams per hour and at higher rates described above.

A TEM micrograph for the particles is shown in FIG. 43. From an analysisof the TEM micrograph, the average particle diameter is about 10 nm.While it was not determined if the particle diameters were altered bythe heat treatment, it is unlikely that significant particle growth, ifany, took place since the heat treated particles had a small averagediameter.

Example 9 Lithium Manganese Oxide; Aerosol Metal Precursors

The synthesis of magnesium oxide/lithiated manganese oxide particlesdescribed in this example was performed by laser pyrolysis. Theparticles were produced using essentially the laser pyrolysis apparatusof FIG. 1, described above, using the reactant delivery apparatus ofFIG. 2.

The manganese chloride (Alfa Aesar, Inc., Ward Hill, Mass.) precursorand lithium chloride (Alfa Aesar, Inc.) precursor were dissolved intodeionized water. The aqueous solution had a concentration of 4 molarLiCl and 4 molar MnCl₂. The aqueous solution with the two metalprecursors was carried into the reaction chamber as an aerosol. C₂H₄ gaswas used as a laser absorbing gas, and Argon was used as an inert gas.O₂, Ar and C₂H₄ were delivered into the gas supply tube of the reactantsupply system. The reactant mixture containing MnCl₂, LiCl, Ar, O₂ andC₂H₄ was introduced into the reactant nozzle for injection into thereaction chamber.

The reactant nozzle had an opening with dimensions of ⅝ in.× 1/16 in.Additional parameters of the laser pyrolysis synthesis relating to theparticles are specified in Table 5.

TABLE 5 1 Crystal Structure Amorphous Pressure (Torr) 450 Argon-Window(SCCM) 700 Argon-Shielding (SLM) 5.6 Ethylene (SLM) 1.27 Argon (SLM)1.46 Oxygen (SLM) 1.07 Laser Output (Watts) 590 Li Precursor 4 M LithiumChloride Mn Precursor 4 M Manganese Chloride Precursor Temperature ° C.Room Temperature sccm = standard cubic centimeters per minute slm =standard liters per minute Argon-Win. = argon flow through inlets 216,218 Argon-Sld. = argon flow through annular channel 142. Argon = Argondirectly mixed with the aerosol

The production rate of manganese oxide/lithiated manganese oxideparticles was typically about 1 g/hr. Based on the teachings herein bothabove and in this example, the particles described in this example canbe produced with equivalent properties in appropriate apparatuses and atappropriate conditions at rates in the range(s) of at least about 35grams per hour and at higher rates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in Table 5 is shown in FIG. 44. The x-raydiffractogram shown in FIG. 44 indicates that the sample was amorphous.In particular, a broad peak from about 27° to about 35° corresponds tothe amorphous lithiated manganese oxide. A sharp peak at about 15° isdue to the presence of a trace amount of manganese chloridecontamination. A sharp peak at 53° is due to a trace amount of anunidentified contaminant.

Example 10 Heat Treatment—Lithium Manganese Oxide

A sample of manganese oxide/lithiated manganese oxide nanoparticlesproduced by laser pyrolysis according to the conditions specified in theExample 9 were heated in an oven under oxidizing conditions. The ovenwas essentially as described above with respect to FIG. 6. Between about100 and about 300 mg of nanoparticles were placed in an open 1 cc vialwithin the quartz tube projecting through the oven. Oxygen gas wasflowed through a 1.0 inch diameter quartz tube at a flow rate of 308cc/min. The oven was heated to about 400° C. The particles were heatedfor about 16 hours.

The crystal structure of the resulting heat treated particles weredetermined by x-ray diffraction. The x-ray diffractogram for heatedsample is shown in FIG. 45. The x-ray diffractogram shown in FIG. 45indicates that the collection of particles involved mixed phase materialwith major components of LiMn₂O₄ (about 60% by volume) and Mn₃O₄ (about30% by volume) and a minor component of Mn₂O₃ (about 10% by volume). TheLiMn₂O₄ compound has a cubic spinel crystal structure. It is possiblethat the sample included additional amorphous phases of materials. Inparticular, based on the amount of lithium introduced in the reactantstream, the sample presumably contains additional lithium that is notidentified in the crystalline phases. Based on the teachings herein bothabove and in this example, the particles described in this example canbe produced with equivalent properties in appropriate apparatuses and atappropriate conditions at rates in the range(s) of at least about 35grams per hour and at higher rates described above.

Example 11 Direct Synthesis of Crystalline Lithium Manganese Oxide withan Aerosol

The synthesis of crystalline lithium manganese oxide particles describedin this example was performed by laser pyrolysis. The particles wereproduced using essentially the laser pyrolysis apparatus of FIG. 1,described above.

Two solutions were formed with manganese nitrate (Mn(NO₃)₂, Alfa Aesar,Inc., Ward Hill, Mass.) precursor, lithium nitrate (Alfa Aesar, Inc.)precursor and urea (CH₄N₂O). The first solution was used to form sample3 of Table 6. The first solution was an aqueous solution with aconcentration of 3 molar LiNO₃ and 4 molar Mn(NO₃)₂. The solvent for thesecond solution was a 50:50 percent by weight mixture of isopropylalcohol and deionized water. The second solution had a concentration of2 molar LiNO₃, 2 molar Mn(NO₃)₂, and 3.6 molar urea. The second solutionwas used to form the first and second samples of Table 6.

The selected solution with the two metal precursors was carried into thereaction chamber as an aerosol. C₂H₄ gas was used as a laser absorbinggas, and Argon was used as an inert gas. O₂, Ar and C₂H₄ were deliveredinto the gas supply tube of the reactant supply system. The reactantmixture containing Mn(NO₃)₂, LiNO₃, Ar, O₂ and C₂H₄ was introduced intothe reactant nozzle for delivery into the reaction chamber. The reactantnozzle had an opening with dimensions of ⅝ in.×¼ in. Additionalparameters of the laser pyrolysis synthesis relating are specified inthe first two columns of Table 6.

TABLE 6 1 2 3 Crystal Structure LiMn₂O₄ LiMn₂O₄ LiMn₂O₄ (major) +(major) + (major) + Mn₃O₄ Mn₃O₄ Mn₃O₄ Pressure (Torr) 600 600 600Argon-Window (SLM) 2.24 2.24 2.24 Argon-Shielding (SLM) 9.86 9.86 9.86Ethylene (SLM) 0.80 0.80 1.24 Argon (SLM) 3.61 3.60 4.17 Oxygen (SLM)0.97 0.99 1.46 Laser Input (Watts) 650 970 380 Laser Output (Watts) 540830 320 Production Rate (gm/hr) 1.8 1.3 17.0 Precursor Temperature ° C.Room Temp. Room Temp. Room Temp. slm = standard liters per minuteArgon-Win. = argon flow through inlets 216, 218 Argon-Sld. = argon flowthrough annular channel 142. Argon = Argon directly mixed with theaerosol

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. X-ray diffractograms for samples produced under theconditions of columns 1 and 2 specified in Table 6 are shown in FIG. 46.This is a representative diffractogram, although some samples hadrelatively small peaks due to Mn₃O₄ contamination. X-ray diffractionpeaks characteristic of spinel lithium manganese oxide are clearlyvisible in the diffractogram. Small differences in stoichiometry withinthe spinel structure are difficult to elucidate from the x-raydiffractogram. In addition, the x-ray diffractogram peaks are broad,which may be due to the small particle size or inhomogeneous broadeningresulting from either having a mixed phase material or variations instoichiometry. Nevertheless, the diffractogram is consistent with thesample containing a mixture of LiMn₂O₄ and Li₄Mn₅O₁₂ or an intermediatestoichiometry material. These conclusions are confirmed byelectrochemical evaluation described below. In any case, the crystallinelithium manganese oxide seems to comprise a majority (greater than about50%) of the material in one form or another.

Transmission electron microscopy (TEM) was used to determine particlesizes and morphology of the as synthesized, crystalline lithiummanganese oxide. A TEM micrograph for the lithium manganese oxide of thesample produced under the conditions of column 2 of Table 6 is shown inFIG. 47. The corresponding particle size distribution is shown in FIG.48. The average particle diameter is about 40 nm. The particle sizedistribution shows a relatively broad particle size distributionrelative to particle size distributions generally obtainable by laserpyrolysis.

Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

Example 12 Heat Processing to Form Silver Vanadium Oxide

This example demonstrates the production of nanoscale silver vanadiumoxide using a vanadium oxide nanoparticle starting material. The silvervanadium oxide is produced by a heat processing.

About 9.5 g of silver nitrate (AgNO₃) was dissolved into about 15 ml ofdeionized water. Then, about 10 g of V₂O₅ nanoparticles produced bylaser pyrolysis were added to the silver nitrate solution to form amixture. The resulting mixture was stirred on a magnetic stirrer forabout 30 minutes. After the stirring was completed the solution washeated to about 160° C. in an oven to drive off the water. The driedpowder mixture was ground with a mortar and pestle. Based on theteachings herein both above and in this example, the particles describedin this example can be produced with equivalent properties inappropriate apparatuses and at appropriate conditions at rates in therange(s) of at least about 35 grams per hour and at higher ratesdescribed above.

Six samples from the resulting ground powder weighing between about 100and about 300 mg of nanoparticles were placed separately into an open Icc boat. The boat was placed within the quartz tube projecting throughan oven to perform the heat processing. The oven was essentially asdescribed above with respect to FIG. 24. Oxygen gas or argon gas wasflowed through a 1.0 in diameter quartz tube at a flow rate of about 20seem. The samples were heated in the oven under the followingconditions:

-   -   1) 250° C., 60 hrs in argon    -   2) 250° C., 60 hrs in oxygen    -   3) 325° C., 4 hrs in argon    -   4) 325° C., 4 hrs in oxygen    -   5) 400° C., 4 hrs in argon    -   6) 400° C., 4 hrs in oxygen.        The samples were heated at approximately the rate of 2° C./min.        and cooled at the rate of approximately 1° C./min. The times        given above did not include the heating and cooling time.

The structure of the particles following heating was examined by x-raydiffraction. The x-ray diffractograms for the samples heated in oxygenand in argon are shown in FIGS. 49 and 50, respectively. All of theheated samples produces diffractograms with peaks indicating thepresence of Ag₂V₄O₁₁. The samples heated at 400° C. appear to lacksignificant amounts of V₂O₅. Heating the samples for somewhat longertimes at the lower temperatures should eliminate any remaining portionsof the V₂O₅ starting material.

A transmission electron micrograph of the silver vanadium oxideparticles is shown in FIG. 51. For comparison, a transmission electronmicrograph of the V₂O₅ nanoparticle sample used to form the silvervanadium oxide nanoparticles is shown in FIG. 52, at the same scale asFIG. 51. The silver vanadium oxide particles in FIG. 51 surprisinglyhave a slightly smaller average diameter than the vanadium oxidenanoparticle starting material in FIG. 52.

Example 13 Direct Laser Pyrolysis Synthesis of Silver Vanadium OxideNanoparticles

The synthesis of silver vanadium oxide nanoparticles described in thisexample was performed by laser pyrolysis. The particles were producedusing essentially the laser pyrolysis apparatus of FIG. 1, describedabove.

Two solutions were prepared for delivery into the reaction chamber as anaerosol. Both solutions were produced with comparable vanadium precursorsolutions. To produce the first vanadium precursor solution, a 10.0 gsample of vanadium (III) oxide (V₂O₃) from Aldrich Chemical (Milwaukee,Wis.) was suspended in 120 ml of deionized water. A 30 ml quantity of70% by weight aqueous nitric acid (HNO₃) solution was added dropwise tothe vanadium (III) oxide suspension with vigorous stirring. Caution wastaken because the reaction with nitric acid is exothermic and liberatesa brown gas suspected to be NO₂. The resulting vanadium precursorsolution (about 150 ml) was a dark blue solution. The second vanadiumprecursor solution involved the scale-up of the first precursor solutionby a factor of three in all ingredients.

To produce a first silver solution, a solution of silver carbonate(Ag₂CO₃) from Aldrich Chemical (Milwaukee, Wis.) was prepared bysuspending 9.2 g of silver carbonate in a 100 ml volume of deionizedwater. A 10 ml quantity of 70% by weight aqueous nitric acid (HNO₃) wasadded dropwise with vigorous stirring. A clear colorless solutionresulted upon completion of the addition of nitric acid. To produce afirst metal mixture solution for aerosol delivery, the silver solutionwas added to the first vanadium precursor solution with constantstirring. The resulting dark blue first metal mixture solution had amolar ratio of vanadium to silver of about 2:1.

To produce a second silver solution, 34.0 g of silver nitrate (AgNO₃)from Aldrich Chemical (Milwaukee, Wis.) was dissolved in a 300 ml volumeof deionized water. To prepare a second solution of metal mixtures foraerosol delivery, the silver nitrate solution was added to the secondvanadium precursor solution with constant stirring. The resulting darkblue second metal mixture solution also had a molar ratio of vanadium tosilver of about 2:1.

The selected aqueous solution with the vanadium and silver precursorswas carried into the reaction chamber as an aerosol. C₂H₄ gas was usedas a laser absorbing gas, and Argon was used as an inert gas. O₂, Ar andC₂H₄ were delivered into the gas supply tube of the reactant supplysystem. The reactant mixture containing vanadium oxide, silver nitrate,Ar, O₂ and C₂H₄ was introduced into the reactant nozzle for injectioninto the reaction chamber. The reactant nozzle had an opening withdimensions of ⅝ in.×¼ in. Additional parameters of the laser pyrolysissynthesis relating to the particle synthesis are specified in Table 7.

TABLE 7 1 2 Crystal Structure Mixed Phase Mixed Phase Pressure (Torr)600 600 Argon-Window (SLM) 2.00 2.00 Argon-Shielding (SLM) 9.82 9.86Ethylene (SLM) 0.74 0.81 Argon (SLM) 4.00 4.80 Oxygen (SLM) 0.96 1.30Laser Power (input) (Watts) 490-531 390 Laser Power (output) (Watts) 445320 Precursor Solution 1 2 Precursor Temperature ° C. Room RoomTemperature Temperature slm = standard liters per minute Argon-Win. =argon flow through inlets 216, 218 Argon-Sld. = argon flow throughannular channel 142. Argon = Argon directly mixed with the aerosol

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. X-ray diffractograms for samples 1 (lower curve) and 2(upper curve) produced under the conditions specified in Table 7 areshown in FIG. 53. The samples had peaks corresponding to VO₂, elementalsilver and peaks that did not correspond to known materials. Asignificant crystalline phase for these samples had peaks at 2Θ equal toabout 30-31°, 32, 33 and 35. This phase is thought to be a previouslyunidentified silver vanadium oxide phase. This phase is observed insamples prepared by mixing vanadium oxide nanoparticles and silvernitrate under conditions where the samples are heated for aninsufficient time period to produce Ag₂V₄O_(ii). Specific capacitymeasurements of sample 1 in a coin cell, presented below, are consistentwith this interpretation.

Powders of samples produced under the conditions specified in Table 7were further analyzed using transmission electron microscopy. The TEMmicrographs are shown in FIGS. 54A (first column of Table 7) and 54B(second column of Table 7). The TEM micrograph has a particles fallingwithin different size distributions. This is characteristic of mixedphase materials made by laser pyrolysis, where each material generallyhas a very narrow particle size distribution. The portion of silvervanadium oxide in the mixed phase material should be increased by anincrease in oxygen flow, a decrease in laser power and an increase inpressure.

Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

Example 14 Production of Elemental Silver Nanoparticles

The synthesis of elemental silver nanoparticles described in thisexample was performed by laser pyrolysis. The particles were producedusing essentially the laser pyrolysis apparatus of FIG. 1.

A 1 molar silver nitrate solution was prepared for delivery into thereaction chamber as an aerosol by dissolving 50.96 g of silver nitrate(Aldrich Chemical, Milwaukee, Wis.) into 300 ml deionized water toproduce a clear solution. C₂H₄ gas was used as a laser absorbing gas,and Argon was used as an inert gas. O₂, Ar and C₂H₄ were delivered intothe gas supply tube of the reactant supply system. The reactant mixturecontaining silver nitrate, Ar, O₂ and C₂H₄ was introduced into thereactant nozzle for injection into the reaction chamber. The reactantnozzle had an opening with dimensions of ⅝ in.×¼ in. Additionalparameters of the laser pyrolysis synthesis relating to the particlesynthesis are specified in Table 8.

TABLE 8 1 2 Crystal Structure face centered cubic face centered cubicPressure (Torr) 450 450 Argon-Window (SLM) 2.00 2.00 Argon-Shielding(SLM) 9.82 9.82 Ethylene (SLM) 1.342 0.734 Argon (SLM) 5.64 3.99 Oxygen(SLM) 1.41 0.96 Laser Power (input) (Watts) 970 490 Laser Power (output)(Watts) 800 450 Production Rate (gram/hour) 1.44 1.02 PrecursorTemperature ° C. Room Temperature Room Temperature slm = standard litersper minute Argon-Win. = argon flow through inlets 216, 218 Argon-Sld. =argon flow through annular channel 142. Argon = Argon directly mixedwith the aerosolBased on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. X-ray diffractograms for sample 1 and sample 2 producedunder the conditions specified in Table 8 are shown in FIGS. 55 and 56,respectively. The samples had strong peaks corresponding to elementalsilver.

Powders produced under the conditions of column 1 of Table 8 werefurther analyzed using transmission electron microscopy. The TEMmicrograph is shown in FIG. 57. The particle size distribution in theTEM micrograph is broad relative to particle size distributionsinvolving laser pyrolysis synthesis. The particle size distribution canbe narrowed significantly by either using gas phase precursors or a moreuniform aerosol delivery.

Representative particles were also analyzed by elemental analysis. Atypical elemental analysis of these materials yielded in weight percentabout 93.09% silver, 2.40% carbon, 0.05% hydrogen, and 0.35% nitrogen.Oxygen was not directly measured and may have accounted for some of theremaining weight. The elemental analysis was performed by DesertAnalytics, Tucson, Ariz.

The carbon component in the nanoparticles likely is in the form of acoating. Such carbon coatings can be formed from the carbon introducedby ethylene within the reactant stream. Generally, the carbon can beremoved by heating under an oxidizing atmosphere under mild conditions.The removal of such carbon coatings is described further in U.S. Pat.No. 6,387,531, entitled “Metal (Silicon) Oxide/Carbon CompositeParticles,” incorporated herein by reference.

Since other group IB elements, copper and gold, have similar chemicalproperties as silver, substitution of copper or gold precursors for thesilver precursors under similar conditions should result in theproduction of elemental copper or gold nanoparticles.

Example 15 Formation of Silicon Nitride Nanoparticles

Silicon nitride particles were produced by laser pyrolysis. The laserpyrolysis was performed in an apparatus essentially as shown in FIG. 10with the batch collection apparatus.

The reactant stream included ammonia (NH₃) and silane (SiH₄) that weredelivered as vapor. The reaction conditions are summarized in Table 9.

TABLE 9 Phase Silicon nitride Crystal Structure amorphous Pressure(Torr) 200 Argon-Win (slm) 5 Argon-Sld. (slm) 30 Ammonia (slm) 3.6-3.8Silane (slm) 2.0 Production Rate 280 (gm/hr) Laser Power - Input 800-1000 (watts) Laser Power - Output 400-500 (watts) slm = standardliters per minuteBased on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

An x-ray diffractogram of the silicon nitride nanoparticles using theCu(Kα) radiation line on a Siemens D500 x-ray diffractometer are shownin FIG. 58. The diffractogram has peaks corresponding to crystallinesilicon nitride as well as a broad peak at low scattering anglesindicative of a larger degree of an amorphous state.

Transmission electron micrographs of the nanoparticles are shown in FIG.59. An approximate size distribution was determined by manuallymeasuring diameters of the particles shown in FIG. 59. The particle sizedistribution is shown in FIG. 60. An average particle size of about 17.6nm was obtained. Only those particles showing clear particle boundarieswere measured and recorded to avoid regions distorted in the micrograph.This should not bias the measurements obtained since the single view ofthe micrograph may not show a clear view of all particles because of theorientation of the particles.

Example 16 Formation of Silicon Carbide Nanoparticles

Amorphous silicon carbide particles were produced by laser pyrolysis.The synthesis was laser pyrolysis apparatus essentially as shown in FIG.1 with a single slit nozzle.

The dimethyl diethoxysilane ((CH₃CH₂O)₂Si(CH₃)₂) (Strem Chemical, Inc.,Newburyport, Mass.) precursor vapor was carried into the reactionchamber by bubbling Ar gas through the dimethoxysilane liquid stored ina container at room temperature. Additional argon was added as a diluentto the reactant stream. The dimehoxysilane decomposes to form thesilicon carbide particles. The reactant gas mixture containingdimethoxysilane, Ar and C₂H₄ (optionally) was introduced into thereactant gas nozzle for injection into the reactant chamber. Thereactant gas nozzle had dimensions ⅝ in×⅛ in. C₂H₄ gas was used,optionally, as a laser absorbing gas for some runs, althoughdimethoxysilane may absorb CO₂ laser radiation sufficiently thatethylene may not be necessary. Argon was used as an inert gas.

Representative reaction conditions for the production of amorphoussilicon carbide nanoparticles are described in Table 10.

TABLE 10 Phase Silicon carbide Silicon carbide Crystal StructureAmorphous Amorphous Pressure (Torr) 410 700 Argon-Win (slm) 2.24 2.24Argon-Sld. (slm) 8.40 8.40 Ethylene (slm) 1.61 0.00 Carrier Gas - Argon1.13 1.97 (slm) Dilution Gas - Argon 1.4 0.0 (slm) Precursor Temp. (°C.) Room Temp. Room Temp. Production Rate 3.0 3.28 (gm/hr) Laser Power -Input 970 1140 (watts) Laser Power - Output 700 1020 (watts) slm =standard liters per minute Argon - Win. = argon flow through inlets 216,218 Argon - Sld. = argon flow through annular channel 142Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

An x-ray diffractogram of product nanoparticles produced under theconditions of column 2 of Table 10 is shown in FIG. 61. Broaddiffraction peaks at low scattering angles are seen corresponding toamorphous structure.

The transmission electron micrograph for the materials used to producethe x-ray diffractogram in FIG. 61 is shown in FIG. 62. An approximatesize distribution was determined by manually measuring diameters of theparticles shown in FIG. 61. The particle size distribution is shown inFIG. 63. An average particle size of about 19.5 nm was obtained. Onlythose particles showing clear particle boundaries were measured andrecorded to avoid regions distorted in the micrograph. This should notbias the measurements obtained since the single view of the micrographmay not show a clear view of all particles because of the orientation ofthe crystals.

Example 17 Production of Lithium Iron Phosphate

This example demonstrates the synthesis of lithium iron phosphate bylaser pyrolysis. These powders are useful as electroactive materials, asdescribed in the following example. Laser pyrolysis was carried outusing a reaction chamber essentially as described above with respect toFIG. 6.

Ammonium phosphate-monobasic (NH₄H₂PO₄) (1.0 molar), lithium chloride(LiCl) (1.0 molar) and ferrous chloride (FeCl₂.4H₂O) (1.0 molar)precursors were dissolved in deionized water. All the precursors wereobtained from Aldrich Chemical Co., Milwaukee, Wis. HCl was added toadjust the pH to a low enough value so that the iron remained in a +2state and so that no precipitate was formed. The pH was between 0 and 2.The solution was stirred for 2-3 hours using a magnetic stirrer. Theaqueous precursor solution were carried into the reaction chamber as anaerosol. C₂H₄ gas was used as a laser absorbing gas, and nitrogen wasused as an inert diluent gas. Molecular oxygen (O₂) was used to maintaina neutral environment in the reaction chamber. The reactant mixturecontaining the precursors, N₂, O₂ and C₂H₄ was introduced into thereactant nozzle for injection into the reaction chamber. Additionalparameters of the laser pyrolysis synthesis relating to the particlesare specified in Table 11.

TABLE 11 1 2 Pressure (Torr) 180 180 Nitrogen F.R.-Window 5 5 (SLM)Nitrogen F.R.- 20 20 Shielding (SLM) Ethylene (SLM) 5 3 Diluent Gas(nitrogen) 12 9.5 (SLM) Oxygen (SLM) 3 3.6 Laser Input (Watts) 750 750Laser Output (Watts) 714 680 Production Rate (g/hr) ~1 g ~1 g PrecursorDelivery Rate 10 50 to Atomizer* (ml/min.) slm = standard liters perminute Nitrogen - Win. = N₂ flow near lens 412. Nitrogen - Sld. = N₂flow through shielding gas opening 462. *A majority of the aerosolprecursor returns down the nozzle and is recycled.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Rigaku Miniflex x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in column 1 of Table 11 is shown in FIG. 64. In thediffiactogram, crystalline phases were identified that corresponded toLiFePO₄. A metallic iron impurity seems to contribute a peak at about45°. Based on the x-ray spectra, the materials produced under theconditions in the first column of Table 11 seemed more crystalline thanthe particles produced under the conditions in the second column ofTable 11 (not shown). Additional peaks may correspond to FeFe₂O₄ fromthe oxidation of Fe⁰ to Fe₃O₄. There may also be some amorphous phases.

Samples of lithium iron phosphate nanoparticles produced by laserpyrolysis according to the conditions specified in Table 11 were heatedin an oven under inert conditions. The oven was essentially as describedabove with respect to FIG. 24. Between about 100 and about 700 mg ofnanoparticles were placed in an open 1 cc alumina boat within the quartztube projecting through the oven. N₂ was flowed through a 1.0 inchdiameter quartz tube at a flow rate of 100 seem. The oven was heated toabout 500° C. The particles were heated for about 3-7 hours. Theseparticles are referred to subsequently as H1 powders. These heat treatedsamples yielded good battery results.

The crystal structure of the resulting heat treated particles wasdetermined by x-ray diffraction. The x-ray diffractogram from the heattreated sample indicates a high degree of crystallinity.

Transmission electron microscopy (TEM) was used to evaluate particlesizes and morphology of the heat treated samples. A TEM micrograph ofthe heat treated sample starting with materials produced under theconditions in the second column of Table 11 is shown in FIG. 65.

Also, BET surface areas were measured for the a particle sample producedby laser pyrolysis under the conditions specified in column 2 of Table11 and for the corresponding heat treated sample. The BET surface areawas determined with an N₂ gas absorbate. The BET surface area wasmeasured with a Micromeritics Tristar 3000™ instrument. The samplesproduced by laser pyrolysis as specified in column 2 of Table 11 had BETsurface areas of 24-25 m²/g. For the heat treated sample, particles hada BET surface area of 11-12 m²/g.

Example 18 Laser Pyrolysis Synthesis of Europium Doped Barium ManganeseAluminum Oxide

This example demonstrates the synthesis of europium doped bariummanganese aluminum oxide by laser pyrolysis. These materials are usefulas blue phosphor material in plasma displays and fluorescent lamps.Laser pyrolysis was carried out using a reaction chamber essentially asdescribed above with respect to FIGS. 6-8.

Europium nitrate (Eu(NO₃)₃.6H₂O) (99.99%, 0.0025 molar) precursor,barium nitrate (Ba(NO₃)₂) (99.999%, 0.0475 molar), aluminum nitrate(Al(NO₃)₂.9H₂O) (99.999%, 0.5 molar), and magnesium nitrate(Mg(NO₃)₂.XH₂O) (99.999%, 0.05 molar) precursors were dissolved indeionized water. All the metal precursors were obtained from Alfa Aesar,Inc., Ward Hill, Mass. The solutions were stirred for 2-3 hours on a hotplate using a magnetic stirrer. The aqueous metal precursor solutionswere carried into the reaction chamber as an aerosol. C₂H₄ gas was usedas a laser absorbing gas, and nitrogen was used as an inert diluent gas.The reactant mixture containing the metal precursors, N₂, O₂ and C₂H₄was introduced into the reactant nozzle for injection into the reactionchamber. Additional parameters of the laser pyrolysis synthesis relatingto the particles are specified in Table 12.

TABLE 12 1 2 Pressure (Torr) 300 180 Nitrogen F.R.-Window 5.0 5.0 (SLM)Nitrogen F.R.- 20.0 32.0 Shielding (SLM) Ethylene (SLM) 5.0 1.5 DiluentGas (nitrogen) 14.0 6.0 (SLM) Oxygen (SLM) 2.7 4.5 Laser Input (Watts)1400 1700 Laser Output (Watts) 1286 1653 Production Rate (g/hr) 0.6 0.7Precursor Delivery Rate 20 10 to Atomizer* (ml/min) slm = standardliters per minute Argon - Win. = argon flow through inlets 216, 218Argon - Sld. = argon flow through annular channel 142. *A majority ofthe aerosol precursor returns down the nozzle and is recycled.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Rigaku Miniflex x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in column 1 and 2 of Table 12 is shown in FIGS. 66and 67, respectively. In each of the samples, crystalline phases wereidentified that corresponded to europium doped barium magnesium aluminumoxide (BaMgAl₁₀O₁₇:Eu) by comparison with the diffractogram ofcommercially available powders. Based on the x-ray spectra, thematerials produced under the conditions in the first column of Table 12seemed more crystalline than the particles produced under the conditionsin the second column of Table 12. Additional peaks corresponding toadditional phases are observed that have not been identified. There maybe some amorphous phases.

Samples of europium doped barium magnesium aluminum oxide nanoparticlesproduced by laser pyrolysis according to the conditions specified inTable 12 were heated in an oven under reducing conditions. Between about100 and about 700 mg of nanoparticles were placed in an open 1 ccalumina boat within an alumina tube projecting through the oven. Amixture of 96.04% argon and 3.96% hydrogen was flowed through a 3.0 inchdiameter quartz tube at a flow rate of 100 sccm. The oven was heated toabout 1300° C. The particles produced under the conditions in column 1of Table 1 were heated for about 2 hours, and the particles producedunder the conditions in column 2 of Table 12 were heated for about 2hours and 30 minutes. These particles are respectively referred to as H1(starting powders were produced under conditions in column 1 of Table12) and H2 (starting powders were produced under conditions in column 2of Table 12).

The crystal structure of the resulting heat treated particles wasdetermined by x-ray diffraction. The x-ray diffractogram for heatedsample H1 is shown in FIG. 68, and the x-ray diffractogram for heatedsample H2 is shown in FIG. 69. Both x-ray diffractograms in FIGS. 68 and69 are similar to each other and correspond to highly crystalline, phasepure samples of europium doped barium manganese aluminum oxide.

Transmission electron microscopy (TEM) was used to evaluate particlesizes and morphology of the heat treated samples. A TEM micrograph ofthe particles of sample H2 is shown in FIG. 70. The uniformity of thematerial can be improved by reducing the reactant density in the laserreaction zone. Also, using chloride salt precursors rather than thenitrate precursors likely would result in more uniform materials basedon experiences.

Also, BET surface areas were measured for the two particle samplesproduced by laser pyrolysis under the conditions specified in columns 1and 2 of Table 12 and for portions of the samples following heattreatment. The BET surface area was determined with an N₂ gas absorbate.The BET surface area was measured with a Micromeritics Tristar 3000™instrument. The samples produced by laser pyrolysis as specified incolumns 1 and 2 of Table 12 had BET surface areas of 11.6 m²/g and 17.8m²/g, respectively. For the heat treated samples, particles from sampleH1 had a BET surface area of 4.41 m²/g, and particles from sample H2 hada BET surface area of 8.44 m²/g.

Example 19 Europium Doped Yttrium Oxide

A europium doped mixed metal oxide nanoparticles have also beenproduced, in which the mixed metal oxide included a stoichiometricamount of rare earth metal. These materials are useful as red phosphormaterial in field emission devices. Laser pyrolysis was carried outusing a reaction chamber essentially as described above with respect toFIGS. 6-8.

Europium nitrate (Eu(NO₃)₃.6H₂O) (99.99%) precursor and yttrium nitrate(Y(NO₃)₂) (99.999%) precursors were dissolved in deionized water. Allthe metal precursors were obtained from Alfa Aesar, Inc., Ward Hill,Mass. The solutions were stirred for 2-3 hours on a hot plate using amagnetic stirrer. The aqueous metal precursor solutions were carriedinto the reaction chamber as an aerosol. C₂H₄ gas was used as a laserabsorbing gas, and argon was used as an inert diluent gas. The reactantmixture containing the metal precursors, N₂, O₂ and C₂H₄ was introducedinto the reactant nozzle for injection into the reaction chamber.Additional parameters of the laser pyrolysis synthesis relating to theparticles of are specified in Table 13.

TABLE 13 1 Pressure (Torr) 250 Argon F.R.-Window 10.0 (SLM) ArgonF.R.-Shielding 8.0 (SLM) Ethylene (SLM) 2.5 Diluent Gas (argon) 12.0(SLM) Oxygen (SLM) 3.55 Laser Input (Watts) 1400 Laser Output (Watts)1110 Production Rate (g/hr) 1.1 Precursor Delivery Rate 11.8 toAtomizer* (ml/min) slm = standard liters per minute Argon - Win. = argonflow through inlets 216, 218 Argon - Sld. = argon flow through annularchannel 142. *A majority of the aerosol precursor returns down thenozzle and is recycled.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Rigaku Miniflex x-raydiffractometer. X-ray diffractograms for two samples produced under theconditions specified in Table 13 are shown in FIG. 71. In each of thesamples, crystalline phases were identified that corresponded toeuropeum doped yttrium oxide (Y_(0.95)Eu_(0.05)O₃) by comparison withpublished diffractogram data, which is indicated by the histogram linesat the bottom of FIG. 71. The similarity of the diffractograms for thetwo samples demonstrates the reproducibility of the laser pyrolysissynthesis.

Example 20 Lithium Cobalt Oxide

This example describes the production of lithium cobalt oxidenanoparticles. Initially, the synthesis of lithium cobalt oxideprecursor particles was performed by laser pyrolysis. Laser pyrolysiswas carried out using a reaction chamber essentially as described abovewith respect to FIGS. 4-6.

Cobalt nitrate (Co(NO₃)₂.6H₂O) (Alfa Aesar, Inc., Ward Hill, Mass.)precursor and lithium nitrate (LiNO₃) (Alfa Aesar, Inc.) precursor weredissolved in deionized water. Two different concentrations of solutionswere used, as specified in Table 14. The aqueous metal precursorsolutions were carried into the reaction chamber as an aerosol. C₂H₄ gaswas used as a laser absorbing gas, and Argon was used as an inert gas.The reactant mixture containing cobalt nitrate, lithium nitrate, Ar, O₂and C₂H₄ was introduced into the reactant nozzle for injection into thereaction chamber. Additional parameters of the laser pyrolysis synthesisrelating to the particles are specified in Table 14.

TABLE 14 1 2 Crystalline Phases cobalt, cobalt oxide cobalt, cobaltoxide (CoO), Li₂CO₃ (CoO), Li₂CO₃ Pressure (Torr) 150 150 ArgonF.R.-Window 5 5 (SLM) Argon F.R.-Shielding 20 20 (SLM) Ethylene (SLM)4.75 4.75 Carrier Gas (Argon) 11 11 (SLM) Oxygen (SLM) 5.1 5.1 LaserInput (Watts) 1200 1200 Laser Output (Watts) 850 920 Production Rate(g/hr) 8.4 2.1 Precursor 1.49 M cobalt nitrate, 0.75 M cobalt nitrate,1.93 M lithium nitrate 0.97 M lithium nitrate slm = standard liters perminute Argon - Win. = argon flow through inlets 216, 218 Argon - Sld. =argon flow through annular channel 142.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cr(Kα) radiation line on a Rigaku Miniflex x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in the first column of Table 1 is shown in FIG. 72.Crystalline phases were identified that corresponded to cobalt metal,cobalt oxide (CoO) and lithium carbonate (Li₂CO₃). The precursorparticles produced under the conditions in the second column of Table 1had an x-ray diffractogram similar to the diffractogram shown in FIG.72.

A sample of lithium cobalt oxide precursor nanoparticles produced bylaser pyrolysis according to the conditions specified in the firstcolumn of Table 1 was heated in an oven under oxidizing conditions. Theoven was essentially as described above with respect to FIG. 24. Betweenabout 100 and about 700 mg of nanoparticles were placed in an open 1 ccboat within the quartz tube projecting through the oven. Air was flowedthrough a 3.0 inch diameter quartz tube at a flow rate of 450 seem. Theoven was heated to about 675° C. The particles were heated for about 5hours. Similarly, a sample produced under the conditions in the secondcolumn of Table 14 was heated at 590° C. for five hours in air. When thesamples were heated at temperatures greater than about 700° C.,significant particle growth was observed. When the particles were heatedat temperatures less than about 500° C. a low temperature phase oflithium cobalt oxide was formed that exhibited a lower specific energyover a four volt lithium battery discharge range.

The crystal structure of the resulting heat treated particles wasdetermined by x-ray diffraction. The x-ray diffractogram for heatedsample from the first column of Table 14 is shown in FIG. 73. The x-raydiffractogram shown in FIG. 73 indicates that the collection ofparticles included crystals of LiCoO₉. LiCoO₂ is reported to have arhombohedral crystal structure.

Transmission electron microscopy (TEM) was used to evaluate particlesizes and morphology of the heat treated samples. A TEM photograph ofthe lithium cobalt oxide particles produced following heat treatment ofprecursor particles formed under the conditions in the first column ofTable 14 are shown in FIG. 74. An examination of a portion of the TEMmicrograph yielded an average particle size of about 40 nm. Thecorresponding particle size distribution is shown in FIG. 75. Theapproximate size distribution was determined by manually measuringdiameters of the particles distinctly visible in the micrograph of FIG.74. Only those particles having clear particle boundaries were measuredto avoid regions distorted or out of focus in the micrograph.Measurements so obtained should be more accurate and are not biasedsince a single view cannot show a clear view of all particles. It issignificant that the particles span a rather narrow range of sizes. Somenecking and agglomeration is observed in the TEM micrographs. Theaverage dimension of nonspherical particles was used in plotting theparticle size distribution.

Also, BET surface areas were measured for the two precursor particlesamples produced by laser pyrolysis under the conditions specified incolumns 1 and 2 of Table 14 and for portions of the samples followingheat treatment. The BET surface area was determined with an N₂ gasabsorbate. The BET surface area was measured with a MicromeriticsTristar 3000™ instrument. The results are shown in Table 15.

TABLE 15 1 1H¹ 2 2H² Surface Area 44 7 101 17 (m²/gm) ¹Sample 1H issample 1 of Table 1 following heat treatment as described above. ²Sample2H is the sample 2 of Table 1 following heat treatment as describedabove.The drop in BET surface area following heat treatment is consistent withgrain growth and agglomeration due to the heating process.

Example 21 Lithium Nickel Oxide

This example describes the production of lithium nickel oxidenanoparticles. Initially, the synthesis of lithium nickel oxideprecursor particles was performed by laser pyrolysis. Laser pyrolysiswas performed using an apparatus essentially as described above withrespect to FIGS. 6-8.

Nickel nitrate (Ni(NO₃)₂.6H₂O) (Alfa Aesar, Inc., Ward Hill, Mass.)precursor and lithium nitrate (LiNO₃) (Alfa Aesar, Inc.) precursor weredissolved in deionized water with concentration as noted in Table 16.The aqueous metal precursor solutions were carried into the reactionchamber as an aerosol. C₂H₄ gas was used as a laser absorbing gas, andArgon was used as an inert gas. The reactant mixture containing nickelnitrate, lithium nitrate, Ar, O₂ and C₂H₄ was introduced into thereactant nozzle for injection into the reaction chamber. Additionalparameters of the laser pyrolysis synthesis relating to lithium nickeloxide precursor particles are specified in Table 16.

TABLE 16 1 Crystalline Phases nickel, nickel oxide (NiO), Li₂CO₃,amorphous phases Pressure (Torr) 150 Argon F.R.-Window 5 (SLM) ArgonF.R.-Shielding 20 (SLM) Ethylene (SLM) 4.75 Carrier Gas (Argon) 12 (SLM)Oxygen (SLM) 5.1 Laser Input (Watts) 1207 Laser Output (Watts) 1010Production Rate (g/hr) 4.9 Precursor 1.54 M nickel nitrate, 2.0 Mlithium nitrate slm = standard liters per minute Argon - Win. = argonflow through inlets 216, 218 Argon - Sld. = argon flow through annularchannel 142.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cr(Kα) radiation line on a Rigaku Miniflex™ x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in Table 16 is shown in FIG. 76. Crystalline phaseswere identified that corresponded to nickel metal, nickel oxide (NiO)and lithium carbonate (Li₂CO₃).

A sample of lithium nickel oxide precursor nanoparticles produced bylaser pyrolysis according to the conditions specified in Table 16 washeated in an oven under oxidizing conditions. The oven was essentiallyas described above with respect to FIG. 24. Between about 100 and about300 mg of nanoparticles were placed in an open 1 cc boat within thequartz tube projecting through the oven. Air was flowed through a 1.0inch diameter quartz tube at a flow rate of 200 cc/min. The oven washeated in air to about 400° C. for about 1 hour and then to about 750°C. for about 3 hours.

The crystal structure of the resulting heat treated particles weredetermined by x-ray diffraction. The x-ray diffractogram for the heatedsample with precursors produced under the conditions listed in Table 16is shown in FIG. 77. The x-ray diffractogram shown in FIG. 77 indicatesthat the collection of particles involved crystals of LiNiO₂.

Example 22 Lithium Nickel Cobalt Oxide

This example describes the production of lithium nickel cobalt oxidenanoparticles. Initially, the synthesis of lithium nickel cobalt oxideprecursor particles was performed by laser pyrolysis. The laserpyrolysis was performed in a reaction chamber essentially as describedabove with respect to FIGS. 6-8.

Nickel nitrate (Ni(NO₃)₂.6H₂O) (Alfa Aesar) precursor, cobalt nitrate(Co(NO₃)₂.6H₂O) (Alfa Aesar) precursor and lithium nitrate (LiNO₃) (AlfaAesar) precursor were dissolved in deionized water at concentrations asnoted in Table 17. The aqueous metal precursor solutions were carriedinto the reaction chamber as an aerosol. C₂H₄ gas was used as a laserabsorbing gas, and Argon was used as an inert gas. The reactant mixturecontaining nickel nitrate, cobalt nitrate, lithium nitrate, Ar, O₂ andC₂H₄ was introduced into the reactant nozzle for injection into thereaction chamber. Additional parameters of the laser pyrolysis synthesisfor producing lithium nickel cobalt oxide precursor particles arespecified in Table 17.

TABLE 17 1 Crystalline Phases nickel, nickel oxide (NiO), LiCO₃,amorphous phases Pressure (Torr) 150 Argon F.R.-Window 5 (SLM) ArgonF.R.-Shielding 20 (SLM) Ethylene (SLM) 4.75 Carrier Gas (Argon) 12 (SLM)Oxygen (SLM) 5.1 Laser Input (Watts) 1207 Laser Output (Watts) 1030Production Rate (g/hr) 3.64 Precursor 1.74 M nickel nitrate, 0.35 Mcobalt nitrate, 2.25 M lithium nitrate slm = standard liters per minuteArgon - Win. = argon flow through inlets 216, 218 Argon - Sld. = argonflow through annular channel 142.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cr(Kα) radiation line on a Rigaku Miniflex™ x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in Table 17 is shown in FIG. 78. Crystalline phaseswere identified that corresponded to nickel metal, nickel oxide (NiO)and lithium carbonate (Li₂CO₃). Some amorphous phase material may alsobe present.

A sample of lithium nickel cobalt oxide precursor nanoparticles producedby laser pyrolysis according to the conditions specified in Table 17 washeated in an oven under oxidizing conditions. The oven was essentiallyas described above with respect to FIG. 24. Between about 100 and about700 mg of nanoparticles were placed in a boat within the quartz tubeprojecting through the oven. Air was flowed through a 1.0 inch diameterquartz tube at a flow rate of 200 cc/min. The oven was heated in air toabout 400° C. for about 1 hour and then to about 675° C. for about 3hours.

The crystal structure of the resulting heat treated particles weredetermined by x-ray diffraction. The x-ray diffractogram for heatedsample with precursors produced under the conditions listed in Table 17is shown in FIG. 79. The x-ray diffractogram shown in FIG. 79 indicatesthat the collection of particles included crystals of lithium nickelcobalt oxide. The precursors were introduced at a concentration totarget a composition of LiNi_(0.8)Co_(0.2)O₂.

Example 23 Lithium Titanium Oxide Nanoparticles

The production of nanoparticles of lithium titanium oxide (Li₄Ti₅O₁₂) isdescribed in this example. The lithium titanium oxide nanoparticles wereproduced in a two step process. In the first step, titanium oxidenanoparticles were produced by laser pyrolysis. In the second step, amixture of titanium oxide nanoparticles and lithium hydroxide wereheated.

The titanium oxide particles were produced using essentially a laserpyrolysis apparatus shown in FIG. 1 of U.S. Pat. No. 5,938,979 to Kambeet al., entitled “Electromagnetic Shielding,” incorporated herein byreference. Titanium tetrachloride (Strem Chemical, Inc., Newburyport,Mass.) precursor vapor was carried into the reaction chamber by bubblingAr gas through TiCl₄ liquid in a container at room temperature. C₂H₄ gaswas used as a laser absorbing gas, and argon was used as an inert gas.The reaction gas mixture containing TiCl₄, Ar, O₂ and C₂H₄ wasintroduced into the reactant gas nozzle for injection into the reactionchamber. The reactant gas nozzle had an opening with dimensions of ⅝in×⅛ in. The production rate of titanium dioxide particles was typicallyabout 4 g/hr. Additional parameters of the laser pyrolysis synthesisrelating to the titanium oxide particles are specified in Table 18.

TABLE 18 1 Crystalline Phases Anatase & Rutile Pressure (Torr) 320 ArgonF.R.-Window 700 (SCCM) Argon F.R.-Shielding 7.92 (SLM) Ethylene (SLM)1.34 Carrier Gas (Argon) 714 (SCCM) Oxygen (SCCM) 550 Laser Output(Watts) 450 Nozzle Size ⅝ in × ⅛ in sccm = standard cubic centimetersper minute slm = standard liters per minute Argon - Win. = argon flowthrough inlets 216, 218 Argon - Sld. = argon flow through annularchannel 142.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cr(Kα) radiation line on a Rigaku Miniflex™ x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in Table 18 is shown in FIG. 80. The titaniumdioxide particles had a crystal structure indicating mixed phases ofanatase titanium dioxide and a small portion of rutile titanium dioxide.The diffractogram has a broad peak at about 23° and at low scatteringangles indicative of amorphous carbon. The amorphous carbon coating canbe removed upon subsequent heating.

Transmission electron microscopy (TEM) was used to determine particlesizes and morphology. A TEM micrograph for the particles produced underthe conditions of Table 18 is displayed in FIG. 81. The particles hadfacets corresponding to the crystal lattice of the titanium oxide.

An elemental analysis of the particles was performed. The particlesincluded 55.18 percent by weight carbon and 19.13 percent by weighttitanium. Chlorine contamination was found to be 0.42 percent by weight.Oxygen was not directly measured but presumably accounted for most ofthe remaining weight. The elemental analysis was performed by DesertAnalytics, Tucson, Ariz.

To produce the lithium titanium oxide particles, 3.67 g LiOH.H₂O (AlfaAesar, Inc., Ward Hill, Mass.) and 8.70 g TiO₂ nanoparticles (asdescribed above) were mixed together using 22.9 g diglyme as adispersant. Other dispersants can be used as long as they do notdissolve either reactant. The mixture was combined with 3 mmyttria-stabilized zirconia grinding media in a polypropylene bottle(Union Process, Akron, Ohio). The slurry with the grinding media wasmixed for two hours in a shaker mill (SPEX Certiprep, Inc., Metuchen,N.J.).

After mixing the slurry was poured through a sieve to remove thegrinding media. The grinding media was rinsed with additional diglyme toremove additional material from the grinding media. Following removal ofthe grinding media, the slurry was vacuum filtered to remove the solventand to collect the power on filter paper. The powder was transferredfrom the filter paper to a glass petri dish.

To remove the remaining solvent, the material was heated at 160° C. for10 hours under vacuum. The solvent was collected in a trap. To performthe conversion of the material to lithium titanium oxide, the driedmaterial was heated in an alumina boat within a one inch tube furnace,as shown schematically in FIG. 24. O₂ is flowed through the tube at arate of 40 cc/min The heat treatment was continued for 20 hours at 800°C. For comparison commercial TiO₂ was processed into Li₄Ti₄O₁₂ in thesame way.

The crystal structures of the resulting heat treated particles weredetermined by x-ray diffraction using the Cr(Kα) radiation line on aRigaku Miniflex™ x-ray diffractometer. The x-ray diffractograms for theheated samples are shown in FIG. 82. The upper curve is thediffractogram obtained from the lithium titanium oxide formed fromcommercial TiO₂, and the lower curve is the diffractogram obtained fromthe lithium titanium oxide formed from nanoparticulate TiO₂. The lineplot at the bottom of FIG. 82 indicates the known positions and relativeintensities of an x-ray diffractogram for Li₄Ti₅O₁₂. From a review ofthe x-ray diffractograms, the synthesized lithium titanium oxideparticles had a stoichiometry corresponding to Li₄Ti₅O₁₂.

A transmission electron micrograph (TEM), shown in FIG. 83, was obtainedfor the lithium titanium oxide nanoparticles. From the TEM photo, theparticles had an average particle diameter of about 200 nm. TEM analysisof the TiO₂ nanoparticles indicated a bimodal distribution of particlesizes with average particles sizes of about 15 nm and about 100 nm. Abimodal distribution is generally indicative of a blend of two types ofparticles with different compositions. It was not know if thedistribution of smaller nanoparticles corresponded to carbon particlesor titanium oxide particles.

Example 24 Laser Pyrolysis Synthesis of Alumina with Aerosol Precursors

This example demonstrates the synthesis of delta-aluminum oxide by laserpyrolysis with an aerosol. Laser pyrolysis was carried out using areaction chamber essentially as described above with respect to FIGS.6-8.

Aluminum nitrate (Al(NO₃)₂.9H₂O) (99.999%, 1.0 molar) precursor wasdissolved in deionized water. The aluminum nitrate precursor wasobtained from Alfa Aesar, Inc., Ward Hill, Mass. The solution wasstirred on a hot plate using a magnetic stirrer. The aqueous metalprecursor solutions were carried into the reaction chamber as anaerosol. C₂H₄ gas was used as a laser absorbing gas, and nitrogen wasused as an inert diluent gas. The reactant mixture containing the metalprecursors, N₂, O₂ and C₂H₄ was introduced into the reactant nozzle forinjection into the reaction chamber. Additional parameters of the laserpyrolysis synthesis relating to the particles are specified in Table 19.

TABLE 19 1 2 Pressure (Torr) 200 180 Nitrogen F.R.- 5 5 Window (SLM)Nitrogen F.R.- 20 34 Shielding (SLM) Ethylene (SLM) 2 1.25 Diluent Gas40 20 (argon) (SLM) Oxygen (SLM) 3.17 3.87 Laser Input 910 1705 (Watts)Laser Output 700 1420 (Watts) Production Rate 1.3 0.7 (g/hr) PrecursorDelivery 2.8 1.8 Rate to Atomizer* (ml/min) Surface Area of 13 26Powders (m²/g) slm = standard liters per minute Argon - Win. = argonflow past windows 412. Argon - Sld. = argon flow through slot 462. *Amajority of the aerosol precursor returns down the nozzle and isrecycled.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Rigaku Miniflex x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in column 1 and 2 of Table 19 are shown in FIG. 84,respectively noted 1 and 2 corresponding to samples 1 and 2. In each ofthe samples, crystalline phases were identified that corresponded todelta-aluminum oxide (Al₂O₃) by comparison with known diffractograms.

Also, BET surface areas were measured for the two particle samplesproduced by laser pyrolysis under the conditions specified in columns 1and 2 of Table 19. The BET surface area was determined with aMicromeritics Tristar 3000™ instrument using an N₂ gas absorbate. Thesamples produced by laser pyrolysis as specified in columns 1 and 2 ofTable 19 had BET surface areas of 13 m²/g and 26 m²/g, respectively.These results suggest that the particles produced under the conditionsin column 2 of Table 19 have a smaller particle size. Impurity levels ofC, H, Cl and N were determined by atomic adsorption to be generally lessthan about 1% by weight.

Transmission electron microscopy (TEM) photographs were obtained ofaluminum oxide nanoparticles produced under the conditions of column 2in Table 19. The TEM micrograph is shown in FIG. 85. The particlesgenerally had a spherical morphology. Transparent shell-type particlesare visible in the micrograph along with dense particles. Adjustment ofthe reaction conditions can be used to obtain uniform dense particles.

Example 25 Laser Pyrolysis Synthesis of Alumina with Vapor Precursors

This example describes the laser pyrolysis synthesis of delta-aluminumoxide using vapor precursors. The reaction was carried out in a chambercomparable to the chamber shown in FIG. 6 with a rectangular inletnozzle with a 1.75 inch×0.11 inch opening for vapor/gaseous reactants.

Aluminum chloride (AlCl₃) (Strem Chemical, Inc., Newburyport, Mass.)precursor vapor was carried into the reaction chamber from a sublimationchamber where N₂ gas was passed over heated aluminum chloride solid. Thereactant gas mixture containing AlCl₃, O₂, nitrogen and C₂H₄ wasintroduced into the reactant gas nozzle for injection into the reactantchamber. C₂H₄ gas was used as a laser absorbing gas. Nitrogen was usedas a carrier gas as well as an inert gas to moderate the reaction.Molecular oxygen was used as an oxygen source. Runs with excess oxygenor stoichiometric amounts of oxygen produced the best powders.

Representative reaction conditions for the production of aluminum oxideparticles with vapor precursors are described in Table 20.

TABLE 20 Sample 3 4 5 6 BET Surface Area 83 137 173 192 Pressure (Torr)120 120 120 120 N₂-Win (slm) 10 10 10 10 N₂-Sld. (slm) 2.8 2.8 2.8 2.8Ethylene (slm) 1.25 0.725 0.725 1.25 Carrier Gas - N₂ (slm) 0.72 0.710.71 0.72 Oxygen (slm) 2.4 0.7 0.7 3.8 Laser Power - Input 1500 772 7601500 (Watts) Laser Power - Output 1340 660 670 1360 (Watts) sccm =standard cubic centimeters per minute slm = standard liters per minuteArgon - Win. = argon flow past windows 412. Argon - Sld. = argon flowthrough slot 462.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

An x-ray diffractogram of product nanoparticles for samples 3-5 producedunder the conditions in Table 20 are shown in FIG. 84 as the top threespectra appropriately labeled. Samples 3-5 had x-ray diffractogramscharacteristic of gamma-aluminum oxide. However, with reduced particlesizes, the diffraction peaks broadened out, as expected, such thatindividual peaks were not resolved. The BET surface areas were measuredas described in Example 24. The values of BET surface area are listed inTable 20. These particles had higher surface areas indicating smallerparticle sizes than the particles produced with aerosol precursors.Impurity levels of C, H, Cl and N were determined by atomic adsorptionto be generally less than about 1% by weight.

A transmission electron micrograph was obtained for a similar aluminumoxide powder produced by laser pyrolysis with vapor precursors having aBET surface area of about 77 m²/g. The micrograph is shown in FIG. 86.The particles had an average particle size well under 100 nm. Also, aTEM micrograph for a sample produced under the conditions of the secondcolumn in Table 20 (sample 4) was obtained. The micrograph is shown inFIG. 87. The particles look highly crystalline with crystal facets beingclearly visible. These particles had an average particle size of lessthan about 20 nm and a very uniform particle size distribution.Calculated surface areas based on the observed particle sizes wereapproximately the same as the measured BET surface areas, indicatingthat the particles were dense, non-porous particles.

Sample 6 produced under the conditions in column 4 of Table 20 wasdelta-aluminum oxide with a carbon coating. The presence of the carboncoating allowed for the heat treating the aluminum oxide particles in areducing atmosphere for the production of alpha-aluminum oxide withoutsintering the particles, as described further below. The production ofmetal oxide particles with carbon coatings is described further in U.S.Pat. No. 6,387,531 to Bi et al., entitled “Metal (Silicon) Oxide/CarbonComposites,” incorporated herein by reference.

Example 26 Heat Treatment of Alumina Particles from Laser Pyrolysis

The starting materials for the heat treatment were aluminum oxideparticles produced under the conditions described in Examples 24 and 25.The heat treatment resulted primarily in the production ofalpha-aluminum oxide from delta-aluminum oxide.

The nanoparticles were heat treated at in a box by placing the samplesin a 2 inch×6 inch alumina crucible. Firing was performed in laboratoryair conditions except for heat treatment with a forming gas. Thenanoparticles were converted by the heat treatment to crystallinealpha-Al₂O₃ particles with some of the samples having a minority portionof theta-Al₂O₃, as described below for specific samples.

A first heat treated sample (H1) was prepared from a delta-aluminumoxide produced as described the second column of Table 19. The samplewas heated as specified in Table 21 and they were cooled by the rate ofthe natural cooling of the furnace when it is turned off

TABLE 21 Sample H1 H2 H3 H4 H5 Temperature 1200 1200 1200 1265 1250 (°C.) Heating 2 12 60 12 3 Time (hours) Heating Rate 15 15 15 15 7 (°C./min.) Gas Ambient Ambient Ambient Ambient Ambient Properties Air AirAir Air Air

The crystal structure of the resulting heat treated particles (H1) wasdetermined by x-ray diffraction. An x-ray diffractogram of sample H1along with a diffractogram of the corresponding powders without heattreatment is presented in FIG. 88. The top diffractogram was producedwith the heat treated material and the lower diffractogram is the samplebefore heat treatment. The heat treatment converted the initiallydelta-aluminum oxide into relatively pure phase alpha-aluminum oxidewith a very small amount of theta-aluminum oxide. Following heattreatment, the particles had a BET surface area of about 12 m²/g. Thedrop in surface area generally would correspond to collapse of thehollow particles into dense particles, although some sintering may alsotake place.

Transmission electron microscopy (TEM) was used to evaluate particlesizes and morphology of the heat treated samples. A TEM micrograph ofsample H1 is shown in FIG. 89. As seen in FIG. 89, not all of the hollowparticles have collapsed into dense particles. The uniformity of thematerial can be improved by reducing the reactant density in the laserreaction zone.

In addition, a sample of delta-aluminum oxide produced with vapor phasereactants by laser pyrolysis was heat treated to generate mixed phasealuminum oxide with a majority alpha-aluminum oxide and some remainingdelta-aluminum oxide and theta aluminum oxide. Three different samples(H2, H3, H4) of the same starting material produced as described inExample 25 were heat treated under conditions specified in Table 21. Thesamples (H2, H3, H4) had BET surface areas of 31 m²/g, 19 m²/g and 7m²/g, respectively. The x-ray diffractograms for the three heat treatedsamples are shown in FIG. 90. The sample with 31 m²/g surface area wasmostly converted to alpha-aluminum oxide, although some delta-aluminumoxide remained. The 7 m²/g sample was pure alpha-aluminum oxide withhigh crystallinity, according to the x-ray diffractogram spectrum.

A TEM micrograph of the 31 m²/g heat treated sample is shown in FIG. 91.Small uniform particles are visible along with larger interconnectedstructures. Selected area diffraction was used to differentiate thedelta-aluminum oxide particles from alpha-aluminum oxide particles.Selected area diffraction of the smaller particles in the TEM micrographindicated that the particles were highly crystalline with d-spacingvalues that matched well with delta-phase or theta-phase crystals.Overall, the sample was roughly 81% alpha-phase.

For comparison, the x-ray diffractogram spectrum of a heat treatedsample (H5) with 22 m²/g surface area is shown in FIG. 92 along with thex-ray diffractogram spectrum of a commercial sample of delta-aluminumoxide from St. Gobain (France) having a BET surface area of 8 m²/g. Theheat treat sample H5 was produced from a sample originally produced bylaser pyrolysis with vapor precursors with heat treatment conditionsspecified in Table 21. The heat treated sample was majorityalpha-aluminum oxide with a small amount of delta-aluminum oxide. Thecommercial sample had unidentified peaks corresponding to an unknowncontaminant. An elemental analysis of the commercial sample identifiedapproximately 9 weight percent contaminants compared with less thanabout 0.5 weight percent for the heat treated laser pyrolysis sample.

Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above.

Example 27 Zinc Oxide Particles

The synthesis of zinc oxide particles described in this example wasperformed by laser pyrolysis. The particles were produced usingessentially the laser pyrolysis apparatus of FIG. 1, described above,using an aerosol delivery apparatus.

The zinc nitrate.6H₂O (Aldrich Chemical Co., Milwaukee, Wis.) precursorwas carried into the reaction chamber as an aerosol of a 4M aqueous zincnitrate solution made with deionized water. C₂H₄ gas was used as a laserabsorbing gas, molecular oxygen was used as an oxygen source, and Argonwas used as an inert gas. The Ar, O₂ and C₂H₄ were supplied as carriergases. The reactant mixture containing Zn(NO₃)₂, Ar, H₂O, O₂ and C₂H₄was introduced into the reactant nozzle for injection into the reactionchamber. The reactant nozzle had an opening with dimensions of ⅝ in.×¼in. Additional parameters of the laser pyrolysis synthesis relating tothe particles are specified in Table 22.

TABLE 22 Crystalline Phase Zinc Oxide (ZnO) + unidentified CrystalStructure Zincite Pressure (Torr) 450 Argon F.R.-Window (SLM) 2.24 ArgonF.R.-Shielding (SLM) 9.86 Ethylene (SLM) 1.42 Argon (SLM) 8.35 Oxygen(SLM) 1.71 Laser Input (Watts) 970 Laser Output (Watts) 770 PrecursorZinc Nitrate solution in water Precursor Molarity 4 M PrecursorTemperature ° C. Room Temperature slm = standard liters per minuteArgon - Win. = argon flow through inlets 216, 218 Argon - Sld. = argonflow through annular channel 142.

The production rate of zinc oxide particles was about 3 g/hr. Based onthe teachings herein both above and in this example, the particlesdescribed in this example can be produced with equivalent properties inappropriate apparatuses and at appropriate conditions at rates in therange(s) of at least about 35 grams per hour and at higher ratesdescribed above.

To evaluate the atomic arrangement, the samples were examined by x-raydiffraction using the Cu(Kα) radiation line on a Siemens D500 x-raydiffractometer. X-ray diffractograms for a sample produced under theconditions specified in Table 22 is shown in FIG. 93. The particles hadan x-ray diffractogram corresponding to zinc oxide, ZnO. The sharp peakin the diffractogram at a value of 2Θ equal to about 22° wasunidentified, indicating that another crystalline phase was present inthe sample. Also, a broad peak centered at a value of 2Θ equal to about18° indicates the presence of an unidentified amorphous phase, possiblyamorphous zinc oxide. Thus, three phases of materials evidently werepresent in the product powders.

An elemental analysis of the product powders yielded 71.55 percent byweight zinc and minor contaminants of 1.68 percent carbon, 0.2 percentnitrogen and 0.08 percent hydrogen. The particles had a gray colorpresumably due to the presence of the carbon. Assuming that theremaining weight is oxygen, the material is somewhat rich in oxygenrelative to ZnO. Previously unknown phases of zinc oxide may be present.The carbon contamination can be removed by heating under mild conditionsin an oxygen atmosphere. The removal of carbon contaminants from metaloxide nanoparticles is described further in copending and commonlyassigned U.S. patent application Ser. No. 09/136,483 to Kumar et al.,entitled “Aluminum Oxide Particles,” incorporated herein by reference.

Based on these results, the reaction conditions can be variedempirically to obtain single phase crystalline ZnO by varying theparameters, such as reactant flow rates, pressure and laserpower/temperature, to locate the conditions for the production of singlephase zinc oxide. Since significant quantities of crystalline ZnO wereproduced under the conditions presented in Table 22, parameters suitablefor production of the single phase material will be similar to theseparameters.

Transmission electron microscopy (TEM) was used to determine particlesizes and morphology. A TEM micrograph for the particles produced underthe conditions of Table 22 is displayed in FIG. 94. The correspondingparticle size distribution is shown in FIG. 95. The approximate sizedistribution was determined by manually measuring diameters of theparticles distinctly visible in the micrograph of FIG. 94. Only thoseparticles having clear particle boundaries were measured to avoidregions distorted or out of focus in the micrograph. Measurements soobtained should be more accurate and are not biased since a single viewcannot show a clear view of all particles. The particle sizedistribution shown in FIG. 95 has a bimodal or trimodal distributionindicative of multiple phases of materials. As noted above, differentphases of materials form different size particles. If the laserpyrolysis is performed under conditions selected to yield a single phaseof product particles, a narrow size distribution should result forparticles of the particular phase. In particular, the resulting singlephase crystalline ZnO would have an extremely narrow particle sizedistribution corresponding roughly to one of the three peak widths fromFIG. 95.

Example 28 Crystalline SnO_(x) (1<x<2), Sample 1

The synthesis of SnO_(x) described in this example was performed bylaser pyrolysis. The SnCl₄ (Strem Chemical, Inc., Newburyport, Mass.)precursor vapor was carried into the reaction chamber by bubbling Ar gasthrough the SnCl₄ liquid in a container at room temperature. C₂H₄ gaswas used as a laser absorbing gas, and Argon was used as an inert gas.The reactant gas mixture containing SnCl₄, Ar, O₂ and C₂H₄ is introducedinto the reactant gas nozzle for injection into the reaction chamber.The reactant gas nozzle has an opening with dimensions as specified inthe first column of Table 23. Additional parameters of the laserpyrolysis synthesis relating to the particles also are specified in thefirst column of Table 23.

TABLE 23 Stoichiometry SnO_(x) SnO_(x) SnO_(x) Crystal TetragonalTetragonal Tetragonal Structure Pressure (Torr) 320 320 180 Argon - Win.700 700 700 (sccm) Argon - Sld. 1.96 1.96 1.96 (slm) Carrier Gas 280(Ar) 280 (Ar) 280 (Ar) (sccm) Ethylene 1206 444 681 (sccm) Oxygen (sccm)554 218 484 Laser Output 380 430 430 (watts) Nozzle Size ⅝ in × ⅛ ⅝ in ×1/16 in ⅝ in × ⅛ in in sccm = standard cubic centimeters per minute slm= standard liters per minute Argon - Win. = argon flow through inlets216, 218 Argon - Sld. = argon flow through annular channel 142

The synthesized tin oxide nanoparticles could be handled directly inair. The production rate of nanoparticles was typically about 5-10 g/hr.Based on the teachings herein both above and in this example, theparticles described in this example can be produced with equivalentproperties in appropriate apparatuses and at appropriate conditions atrates in the range(s) of at least about 35 grams per hour and at higherrates described above. Under the conditions specified in the firstcolumn of Table 23, crystalline SnO_(x) was produced. To evaluate thecrystal lattice, the samples were examined by x-ray diffraction usingthe Cu(Kα) radiation line on a Siemens D500 x-ray diffractometer. Thex-ray diffractogram is displayed in FIG. 96. More than 10 peaksindicative of a crystalline phase were observed between 18 and 60degrees. Transmission electron microscopy (TEM) was used to determineparticle sizes and morphology. A TEM micrograph is displayed in FIG. 97.

An examination of a portion of the TEM micrograph yielded an averageparticle size of about 20 nm. The corresponding particle sizedistribution is shown in FIG. 98. Behind the nanoparticles, images ofcarbon films used to hold the nanoparticles can be seen. The approximatesize distribution was determined by manually measuring diameters of theparticles distinctly visible in the micrograph of FIG. 98. Only thoseparticles having clear particle boundaries were measured, to avoidregions distorted or out of focus in the micrograph. Measurements soobtained should be more accurate and are not biased since a single viewin the micrograph cannot show a clear view of all particles because ofthe orientation of the crystals. It is significant that the particlesspan a rather narrow range of sizes.

The tin oxide nanoscale sample evidently contained some residual tinchlorides, SnCl₂. This was evident from dark regions in the micrographas well as the appearance of certain lines in the x-ray diffractogram.Nevertheless, the tin chlorides were distinct materials not disturbingthe tin oxide lattice as is evident by the crystallinity of the sampleand the distinct identification of specific lines in the diffractogramwith the tin chlorides and other lines with the tin oxides. The specificlines in the diffractogram corresponding to tin oxide could beassociated with a tetragonal lattice. The pattern of lines, however,could not be associated with any known tin oxide material or combinationof known materials (mixed phase). Evidently, the nanoparticles producedhave a stoichiometry and/or lattice structure different from known tinoxide materials. Removing the contributions to the diffractogram fromSnCl₂, diffraction peaks due to the new tin oxide material can beidentified. These peaks from the new tin oxide material are plotted inFIG. 99.

Example 29 SnO_(x) (1<x<2), Sample 2

These particles were produced using a similar laser pyrolysis apparatusas described in Example 28. For the production of particle described inthis example, the reactant gas nozzle had dimensions of ⅝ in× 1/16 in.The reaction conditions used to produce the particles of this exampleare presented in the second column of Table 23.

An x-ray diffractogram of representative product nanoparticles is shownin FIG. 100. Clear diffraction peaks corresponding to a tetragonalcrystalline structure are visible. The diffractogram in FIG. 100 is verysimilar to the diffractogram in FIG. 96 indicating that the crystalsinvolved the same underlying lattice and stoichiometry. The peaks inFIG. 100 are sharper than in FIG. 96 indicating that the particles usedto obtain FIG. 100 has a larger particle size and/or a higher degree ofcrystallinity.

TEM micrographs at high magnification were obtained for the particles inthis example, as shown in FIG. 101. Again, the particles span a rathernarrow range of sizes. In this case, the largest to smallest particlesdiffer by no more than about 15 nm in diameter. An average particle sizeof about 45 nm was obtained. Based on the teachings herein both aboveand in this example, the particles described in this example can beproduced with equivalent properties in appropriate apparatuses and atappropriate conditions at rates in the range(s) of at least about 35grams per hour and at higher rates described above.

Example 30 Crystalline SnO_(x), Sample 3

The experimental arrangement for the production of the nanoparticlesdescribed in this example was the same as that described in Example 28.The reaction conditions are given in the third column of Table 23. Asignificant difference in the laser pyrolysis conditions used to producethe nanoparticles of this Example relative to the conditions used toproduce the nanoparticles of Examples 28 and 29 were the use of a lowerchamber pressure.

The x-ray diffractogram for this material is shown in FIG. 102. Comparedwith the diffractograms in FIGS. 96 and 100, the diffractogram in FIG.102 had several extra peaks. These peaks may arise from residual tinchloride. This possibility is supported by the TEM image, as shown inFIG. 103. Some residual tin chloride can be seen as dark images coveringsome of the particles. From an examination of the micrograph, theaverage particle size was around 30 nm. Based on the teachings hereinboth above and in this example, the particles described in this examplecan be produced with equivalent properties in appropriate apparatusesand at appropriate conditions at rates in the range(s) of at least about35 grams per hour and at higher rates described above.

Example 31 Crystalline SnO₂, Oven Processed

A sample of crystalline SnO_(x) as described in Example 28 was baked inan oven under oxidizing conditions. The oven was essentially asdescribed in FIG. 24. The samples were baked in the oven at about 300°C. for about 12 hours. Oxygen gas flowed through a 1.0 in diameterquartz tube at a flow rate of about 106 sccm. Between about 100 andabout 300 mg of nanoparticles were placed in an open 1 cc vial withinthe quartz tube projecting through the oven. The resulting nanoparticleswere single phase SnO₂ (Cassiterite) nanoparticles. The correspondingx-ray diffractogram is presented in FIG. 104.

A TEM micrograph of these nanoparticles is shown in FIG. 105. A uniformsize and shape was obtained again. The average particle diameter wasabout 20 nm. The particle size distribution is depicted in FIG. 106. Thedistribution in FIG. 106 is very similar to the distribution in FIG. 98,indicating that little if any sintering of the particles occurred. Basedon the teachings herein both above and in this example, the particlesdescribed in this example can be produced with equivalent properties inappropriate apparatuses and at appropriate conditions at rates in therange(s) of at least about 35 grams per hour and at higher ratesdescribed above.

Example 32 Erbium Doped Silica Glass

This example describes the coating of a silicon substrate with a silicaglass including alumina and sodium oxide glass formers and an erbiumdopant using light reactive deposition and consolidation.

Particle coating was performed using light reactive deposition in whichwafer coating was performed within the reaction chamber by sweeping thesubstrate through a product particle stream. The wafer was a siliconwafer with a thermal oxide under-cladding. The apparatus used to coat asubstrate/wafer in the reaction stream is comparable to the apparatusshown in FIGS. 20-22 with an aerosol precursor delivery system. Thecoating was performed with a static coating configuration. Anoxygen/ethylene flame was started first. Then, the aerosol flow wasstarted. When a stable process flame was observed, the wafer wastranslated into the coating position about 17 inches above the laserbeam. At this distance, the product particle flow has spread such thatthe entire surface is simultaneously coated approximately uniformly. Thewafer was left in the flow for about 20 minutes.

A solution was formed combining 66 grams (g) tetraethoxysilane(Si(OC₂H₅)₄ or TEOS, 99.9% pure), 25.6 g aluminum nitrate(Al(NO₃)₃.9H₂O, >98% pure), 9.5 g sodium nitrate (NaNO₃, 99% pure), and1.9 g erbium nitrate (Er(NO₃)₃.5H₂O, 99.99% pure) in a isopropyl alcohol(530 g, 99.5% pure)/water (250 g) solvent mixture. An aerosol of thesolution was carried into the reaction chamber along with argon,ethylene and molecular oxygen gasses. Argon gas was mixed with thereactant stream as a diluent/inert gas to moderate the reaction. C₂H₄gas was used as a laser absorbing gas. O₂ was used as an oxygen source.

The reaction conditions for the production of the powder coatingcoatings are described in Table 24. Flame temperature was measured usingthree thermo-couples located in the flow about 1 inch above the laserbeam.

TABLE 24 Pressure (Torr) 180 Ethylene (slm) 0.75 Oxygen (slm) 3.7 ArgonDilution Gas 6 (slm) Precursor Flow 20 (ml/min) Laser Power - Input 815(watts) Flame Temperature 1100 (° C.) slm = standard liters per minute

Following completion of the coating run, the wafers have a coatingacross the surface of the wafer. The chemical composition of the coatingwas measured using Energy Dispersive X-Ray Analysis (EDXA, OxfordInstruments Model 7021) attached to a Hitachi S-3000H scanning electronmicroscope, which was used for microscopy. The EDXA scans were acquiredat 500× magnification using a 20 kV accelerating voltage and a Wfilament operating at about 85 mA current. The interaction volume wasestimated to have a diameter of approximately 2 microns. EDXA scans weretaken on the coated surface. The powder coating had the followingcompositions as measured by EDXA: O—49.1 weight percent (wt %), Si—31.7wt %, Na—9.9 wt %, Al—5.1 wt %, Er 2.4 wt %, and impurity (C, H, N etc.)total 2.2 wt %. Based on the teachings herein both above and in thisexample, the particles described in this example can be produced withequivalent properties in appropriate apparatuses and at appropriateconditions at rates in the range(s) of at least about 35 grams per hourand at higher rates described above.

The coated wafers were heated in a muffle furnace (Neytech, ModelCenturion Qex). The wafers were first heated at 650° C. in an oxygenatmosphere to remove carbon contaminants and then at 975° C. in a heliumatmosphere to complete consolidation of the glass. Along with theheating and cooling conditions, the heat processing is summarized inTable 25.

TABLE 25 Gas Ramp Hold Heating Flow Rate Target Time Segment Gas (sccm)(C/min) Temp (hours:mins) 1 O₂ 250 50 650 — 2 O₂ 250 — 650 0:10 3 He 25010 975 — 4 He 250 — 975 1 5 He 250 −100 100 — sccm—standard cubiccentimeters per minute

After being removed from the oven, the wafers had a clear glass on theirsurface. The consolidated glass had a thickness from about 4 microns toabout 6 microns. The consolidated glass was found to have the followingcompositions by EDXA analysis: O—50.2 wt %, Si—34.1 wt %, Na—10.5 wt %,Al—3.7 wt %, Er—1.5 wt %, and total impurities 0.1 wt %.

As utilized herein, the term “in the range(s)” or “between” comprisesthe range defined by the values listed after the term “in the range(s)”or “between”, as well as any and all subranges contained within suchrange, where each such subrange is defined as having as a first endpointany value in such range, and as a second endpoint any value in suchrange that is greater than the first endpoint and that is in such range.

The embodiments described above are intended to be illustrative and notlimiting. Additional embodiments are within the claims. Although thepresent invention has been described with reference to preferredembodiments, workers skilled in the art will recognize that changes maybe made in form and detail without departing from the spirit and scopeof the invention.

1. A method for the synthesis of selected inorganic submicron particles,the method comprising: reacting a silicon precursor and a dopantprecursor within a flow through a reaction chamber to form productparticles, wherein the precursors are delivered through one or moreinlets into the reaction chamber; and collecting the product particlesin a collector wherein the product particles comprise doped siliconparticles having an average particle size no more than about 250 nm. 2.The method of claim 1 wherein the reacting of the precursors is drivenby a light beam.
 3. The method of claim 2 wherein the light beam isgenerated by a laser.
 4. The method of claim 3 wherein the laser is aninfrared laser.
 5. The method of claim 2 wherein the inlet has anelongated shape that generates an elongated flow aligned to pass theelongated flow through the light beam.
 6. The method of claim 5 whereinthe reactant inlet nozzle comprises an inlet opening that is elongatedwith an aspect ratio of at least about
 5. 7. The method of claim 1wherein the reacting of the flow is driven thermally through thedelivery of heat energy to the flow.
 8. The method of claim 1 whereinthe dopant comprises B, Al, Ga, In, or combinations thereof.
 9. Themethod of claim 1 wherein the dopant comprises P, Sb or combinationsthereof.
 10. The method of claim 1 wherein the product particles have adopant concentration from about 0.001 to about 5 mole percent.
 11. Themethod of claim 1 wherein the flow of the precursors comprises a vaporprecursor and an aerosol precursor.
 12. The method of claim 1 whereinthe silicon precursor and the dopant precursors are delivered into areaction chamber as vapors.
 13. The method of claim 1 wherein theproduct particles are crystalline.
 14. The method of claim 1 wherein thechamber pressure during the reaction is from about 80 Torr to about 650Torr.
 15. The method of claim 1 wherein the collector is associated witha collection system connected to the reaction chamber such that the flowof product particles enters the collection system.
 16. The method ofclaim 1 wherein the product particles can be harvested from thecollection system in a continuous operation mode.
 17. The method ofclaim 1 wherein the product particles comprise effectively no particleswith a primary particle diameter greater than about 4 times the averageparticle diameter.
 18. The method of claim 1 wherein at least about 95percent of the product particles have a primary particle diametergreater than about 60 percent of the average primary particle diameterand less than about 140 percent of the average primary particlediameter.
 19. A method for the synthesis of selected inorganic submicronparticles, the method comprising: reacting a germanium precursor and adopant precursor within a flow through a reaction chamber to formproduct particles, wherein the precursors are delivered through one ormore inlets into the reaction chamber; and collecting the productparticles in a collector wherein the product particles comprise dopedgermanium particles having an average particle size no more than about250 nm.